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United States Patent |
6,069,196
|
Akao
,   et al.
|
May 30, 2000
|
Molded articles for photographic photo-sensitive materials
Abstract
A molded article for photographic photosensitive material formed of a
molding resin composition consisting essentially of 100 parts by weight of
crystalline resin composition comprising crystalline resin and at least
lubricant or antistatic agent, 0.001 to 2 parts by weight of antioxidant
and 5 to 90 parts by weight of acrylic acid copolymer resin, and a molded
article for photographic photosensitive materials formed of a
light-shielding thermoplastic resin composition comprising a
light-shielding material of which the surface has been treated with a
surface-treating material and antioxidant. The molded article can inhibit
bleeding out and thermal decomposition of antistatic agent, lubridant and
organic nucleating agent, and can prevent various troubles induced
therefrom.
Inventors:
|
Akao; Mutsuo (Kanagawa, JP);
Osanai; Hiroyuki (Kanagawa, JP)
|
Assignee:
|
Fuji Photo Film Co., Ltd. (Kanagawa, JP)
|
Appl. No.:
|
225472 |
Filed:
|
January 6, 1999 |
Foreign Application Priority Data
| May 11, 1992[JP] | 4-117758 |
| Jun 19, 1992[JP] | 4-161029 |
Current U.S. Class: |
524/424; 524/107; 524/315; 524/399; 524/430; 524/442; 524/492 |
Intern'l Class: |
C08K 005/10; C08K 005/04; C08K 003/18 |
Field of Search: |
524/107,315,399,424,430,442,492
|
References Cited
Foreign Patent Documents |
62-172344 | Jul., 1987 | JP.
| |
63-193144 | Aug., 1988 | JP.
| |
1209134 | Aug., 1989 | JP.
| |
2-72347 | Mar., 1990 | JP.
| |
2119707 | Nov., 1983 | GB.
| |
Other References
Database WPI, 89-283461, Derwent Publications Ltd. London GB; &
JP-A-1209134 (FUJI) Aug. 22, 1989 (abstract),
Database Japio, No. 88-193144, Orbit Search Service, CA, US; &
JP-A-63193144(FUJI) Aug. 8, 1988 (abstract).
|
Primary Examiner: Sanders; Kriellion A.
Attorney, Agent or Firm: Sughrue, Mion, Zinn, Macpeak & Seas, PLLC
Parent Case Text
This is a divisional of application Ser. No. 08/059,265 filed May 11, 1993,
the disclosure of which is incorporated herein by reference.
Claims
What is claimed is:
1. A molded article for photographic photosensitive materials formed of a
molding resin composition comprising 100 parts by weight of a crystalline
resin composition comprising not less than 20 parts by weight of
crystalline resin and at least one lubricant or antistatic agents 0.001 to
2 parts by weight of an antioxidant, 0.01 to 30 parts by weight of a
light-shielding material and 5 to 90 parts by weight of an acrylic acid
copolymer resin,
wherein the light-shielding material is carbon black having a pH of 6 to 9
and a mean particle size of 10 to 120 .mu.m, the surface of which is
coated with a surface coating material, and the resin composition contains
phenolic antioxidant.
2. The molded article of claim 1 wherein the crystalline resin is a
polyolefin resin.
3. The molded article of claim 1 which contains vitamin E as an
antioxidant.
4. The molded article of claim 1 wherein the light-shielding material is
furnace carbon black having a pH of 6 to 9, a mean particle size of 10 to
120 .mu.m, a volatile component of not more than 2% and an oil absorption
value of not less than 50 ml/100 g.
5. The molded article of claim 1 which contains 0.01 to 2 parts by weight
of a fatty acid metal salt.
6. The molded article of claim 1 which contains an ethylene-propylene
rubber.
7. The molded article of claim 1 which contains a silicone oil.
8. The molded article of claim 1 which contains 0.01 to 10 parts by weight
of inorganic material having ion-exchange ability.
9. The molded article of claim 1 which contains 0.01 to 30 parts by weight
of oil-absorptive material having an oil absorption value of not less than
50 ml/100 g.
10. The molded article of claim 1 which contains a phenolic antioxidant and
a phosphorus-containing antioxidant in an amount 0.001 to 2 parts by
weight in total.
11. The molded article of claim 1 which is a container body for a
photographic film formed of a polyolefin resin composition comprising not
less than 50 parts by weight of a homopolyethylene resin, an
ethylene-.alpha.-olefin copolymer resin or a combination thereof having a
melt flow rate of 5 to 60 g/10 min, a density of 0.941 to 0.985
g/cm.sup.3, a crystallinity of not less than 75%, a bending elastic
modulus of not less than 6,000 kg/cm.sup.2, a Shore hardness of not less
than 60D, a notched Izod impact strength of not less than 2.0 kg- cm/cm, a
Vicat softening point of not less than 110.degree. C. and a melting point
of not less than 125.degree. C., 0.01 to 5 parts by weight of a nucleating
agent, and 0.001 to 2 parts by weight of an antioxidant, radical scavenger
or a combination thereof.
12. The molded article of claim 1 which is a container body for a
photographic film formed of a polyethylene resin composition having a haze
of not more than 50% comprising not less than 50 parts by weight of a
homopolyethylene resin, an ethylene-.alpha.-olefin copolymer resin or a
combination thereof having a melt flow rate of 5 to 80 g/10 min, a density
of 0.941 to 0.985 g/cm.sup.3, a crystallinity of not less than 75% and a
bending rigidity of not less than 6,000 kg/cm.sup.2, and 0.01 to 5 parts
by weight of an organic nucleating agent consisting of an eutectic
compound of a carboxylic acid having a number of carbon atoms of not less
than 3 and a nitrogen-containing heterocyclic compound having an amino
group or a hydroxyl group at the .alpha.-position, an alicyclic carboxylic
acid amide compound of a divalent or polyvalent aliphatic amine, or a
combination thereof.
13. The molded article of claim 1 containing a member selected from the
group consisting of an oxygen scavenger, a deodorant, a moisture absorber,
a drip-proofing agent and an inorganic material having an ion-exchange
ability.
14. The molded article of any of claim 11 or 12 which is a container for a
photographic film having a haze of not more than 50% containing 0.01 to 5
parts by weight of a nucleating agent and not less than 70 parts by weight
of a homopolyethylene resin, an ethylene-.alpha.-olefin copolymer resin or
a combination thereof having a crystallinity of not less than 75%.
15. The molded article of claim 1 wherein the surface-coating material is a
member selected from the group consisting of a lubricant, an antistatic
agent, a drip-proofing agent, a hydrous aluminum oxide, a hydrous silicon
dioxide, a divalent to tetravalent alcohol, a surfactant, an organic metal
chelate compound, a coupling agent, a hydrocarbon having a softening point
of not more than 90.degree. C. and a silicone oil.
16. The molded article of claim 13 which contains two or more kinds of
thermoplastic resins having a softening point difference of not less than
10.degree. C.
17. The molded article of claim 13 which is formed of a light-shielding
thermoplastic resin composition containing a carbon black having an oil
absorption value of not less than 50 ml/100 g, a volatile component
content of not more than 3.5% and a sulfur content of not more than 0.09%,
the surface of which is coated with a surface-coating material, a
thermoplastic resin and a phenolic antioxidant.
18. The molded article of claim 1 which contains 0.001 to 0.5 parts by
weight of an ester of an aliphatic monocarboxylic acid having a number of
carbon atoms of 20 to 40 and a monovalent aliphatic alcohol having a
number of carbon atoms of 20 to 40.
Description
BACKGROUND OF THE INVENTION
This invention relates to molded articles for photographic photosensitive
materials.
As the molded articles for photographic photosensitive materials, there are
packaging films for photographic photosensitive materials, containers for
a photographic film cartridge and the like.
A conventional packaging film for photographic photosensitive materials is
disclosed in Japanese Patent KOKOKU No. 63-26697, and is composed of a
polyester layer, an adhesive layer, an aluminum foil and a polyolefin
resin layer containing light-shielding material and nonionic antistatic
agent laminated in this order from the outside. Another conventional
packaging film for photosensitive materials is disclosed in Japanese
Patent KOKOKU No. 2-2700, and contains at least one light-shielding film
layer comprising a polymer belonging to polyethylene and more than 1 wt. %
of light-shielding material, and more than 50 wt. % of the total polymers
belonging to polyethylene is L-LDPE resin. The packaging film is excellent
in physical strength and heat sealing properties.
A conventional container body for a photographic film cartridge is
disclosed in Japanese Patent KOKAI No. 61-73947, and is formed of a resin
composition of polypropylene resin containing 0.05 to 1 wt. % of fatty
acid amide lubricant. The container body has various advantages, such as
sharp shortening of injection molding cycle, sharp decrease of molding
troubles, excellent in slipping character between the container bodies
resulting in rare occurrence of abrasion, etc. Another conventional
container body for a photographic film cartridge is disclosed in Japanese
Utility Model KOKOKU No. 2-33236, and is formed of a polypropylene resin
having specific properties containing 0.1 to 3 wt. % of light-shielding
material. The container body has also various advantages, such as
shortening of injection molding cycle, sharp decrease of molding troubles,
great improvement in dropping strength, etc.
However, the above conventional packaging films and cotainer bodies have
various problems caused by the migration of antistatic agent or lubricant
to the surface of the molded article due to the use of crystalline resin.
Moreover, in the case of the container bodies requiring transparency,
organic nucleating agent is blended in order to improve the transparency
(Japanese Patent KOKOKU No. 4-58616), and they have various problems
caused by the migration to the surface or thermal decomposition of the
organic nucleating agent. That is, the above packaging films are inferior
in the permanence of antistatic properties, and antistatic agent gradually
bleed out to induce greasiness, blocking, defective heat seal and the
like. When the blending amount of light-shielding material is much,
various problems occur, such as adverse affect upon photographic
properties, increase of lump generation, defective light-shielding by
pinholes generated by the shaking during conveying, and the like.
In the conventional transparent container bodies, fatty acid amide
lubricant gradually bleed out of the surface resulting in the decrease of
transparency, in the generation of white powder or the like. Organic
nucleating agent, antistatic agent and lubricant tend to be oxidized and
to decompose with heat in molten resin at a high temperature, and
adversely affect photographic photosensitive materials, such as fogging or
sensitivity deviation. Lumps and coloring troubles also occur to degrade
appearance of molded articles. When the blending amount of light-shielding
material is much, various problems occur, such as generation of lumps due
to insufficient dispersion of light-shielding material, decrease of
dropping strength, degradation of photographic properties, such as fogging
and sensitivity deviation. These are particularly problems as the
container body for a high sensitivity photographic negative film not less
than ISO photographic speed 100.
SUMMARY OF THE INVENTION
An object of the invention is to provide a molded article for photographic
photosensitive materials capable of inhibiting bleeding out and thermal
decomposition of antistatic agent, lubricant and organic nucleating agent,
and capable of preventing various troubles induced therefrom.
Another object of the invention is to provide a molded article for
photographic photosensitive materials having a good dispersibility of
light-shielding material, small reduction of physical strength, excellent
photographic properties, no occurrence of lumps, excellent appearance and
complete light-shielding, even though the blending amount of the
light-shielding material is much, with ensuring the excellent properties
of the above conventional molded articles.
The present invention provides a molded article, which has achieved the
above object, formed of a molding resin composition consisting essentially
of 100 parts by weight of crystalline resin composition comprising
crystalline resin and at least lubricant or antistatic agent, 0.001 to 2
parts by weight of antioxidant and 5 to 90 parts by weight of acrylic acid
copolymer resin.
The present invention also provides a molded article, which has also
achieved the above object, formed of a light-shielding thermoplastic resin
composition comprising a light-shielding material of which the surface has
been treated with a surface-treating material and antioxidant.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 through 9 are partial sectional views of packaging films for
photographic photosensitive materials embodying the invention,
respectively.
FIGS. 10 and 11 are sectional views of a cap separated from body-type
container for a photographic film embodying the invention.
FIG. 12 is a perspective view of a cap-body integrated type container for a
photographic film embodying the invention.
FIG. 13 is a front view of a spool for a photographic film embodying the
invention.
FIG. 14 is an exploded perspective view of a photographic film cartridge
made of resin embodying the invention.
FIG. 15 is an exploded perspective view of a photographic film unit with
lenz embodying the invention.
FIG. 16 is a sectional view of a cap-body integrated type case for a
photographic film embodying the invention.
FIG. 17 is an exploded perspective view of a photographic film cartridge
embodying the invention.
FIG. 18 is a perspective view illustrating a packaging process of a package
of a roll photographic photosensitive material using a light-shielding
film provided with a light-shielding thermoplastic resin film layer
embodying the invention.
1a . . . Light-shielding thermoplastic resin film layer (molded article for
photographic photosensitive materials)
2,2a . . . Thermoplastic resin film layer
3,3a . . . Intermediate layer
4 . . . Adhesive layer
5 . . . Flexible sheet layer
9 . . . Metallized biaxially stretched film layer
10 . . . Metal foil
a . . . indicating to contain light-shielding material
DETAILED DESCRIPTION OF THE INVENTION
The crystalline resin used in the invention contains one or more of
homopolyethylene resin, such as low density polyethylene (LDPE) resin,
medium density polyethylene (MDPE) resin and high density polyethylene
(HDPE) resin, homopolypropylene resin, propylene- -olefin copolymer resin
(random type, block type), ethylene copolymer resin, polyacetal resin,
polyamide resin, polyester resin, such as polyethylene terephthalate
resin, polyethylene naphthalate resin, polytetrafluoroethylene resin,
polyvinyl alcohol resin, or isotactic polystyrene resin, in an amount of
more than 50 wt. % in the total. Preferable resins are polyethylene resins
and polypropylene resins, particularly preferably LDPE resin, HDPE resin,
L-LDPE resin and propylene-ethylene copolymer resin.
Suitable ethylene copolymer resins are ethylene-vinyl acetate copolymer
(EVA) resin, ethylene-propylene copolymer resin, ethylene-1-butene
copolymer resin, ethylene-butadiene copolymer resin, ethylene-vinyl
chloride copolymer resin, ethylene-methylmethacrylate copolymer resin,
ethylene-methyl acrylate copolymer (EMA) resin, ethylene-ethyl acrylate
copolymer (EEA) resin, ethylene-acrylonitrile copolymer resin,
ethylene-acrylic acid copolymer (EAA) resin, ionomer resin (copolymer of
ethylene and unsaturated acid crosslinked using metal such as zinc),
ethylene- -olefin copolymer (L-LDPE) resin, ethylene-propylene-butene-1
ternary copolymer resin, ethylene-propylene resin elestomer, and the like.
L-LDPE resin is called third polyethylene resin, and it is a low cost high
strength resin, having the advantages of both low, medium density
polyethylene resin and high density polyethylene resin, which congruent
the requirements, i.e. resource conservation and energy conservation, of
the times. The L-LDPE resin is a copolymer of ethylene and .alpha.-olefin,
and it has a linear structure having short branched. The ethylene content
is 85 to 99.5 mol. %, and the number of carbon atoms of the .alpha.-olefin
is 3 to 13. Preferable .alpha.-olefin has a number of carbon atoms is 4 to
10, and examples of the .alpha.-olefin are butene-1, 4-methylpentene-1,
hexene-1, heptene-1, octene-1 and decene-1. The density is usually in the
degree of low, medium polyethylene resin and most of commercial resins are
in the range of 0.87 to 0.97 g/cm.sup.3. Melt flow rate (ASTM D-1238) is
mostly in the range of 0.1 to 80 g/10 minutes.
As the polymerization process of L-LDPE resin, there are the vapor process
and the liquid slurry process using a medium, low pressure apparatus and
the ion polymerization process using an apparatus for the high pressure
modified method.
Examples of commercial L-LDPE resin are "G-Resin" and "TUFLIN" (UCC), "NUC
Polyethylene-LL" and "TUFTHENE" (Nippon Unicar), "Idemitsu Polyethylene-L"
and Moretec (Idemitsu Petrochemical), "Dowlex" (Dow chemical), "Suclear"
(Dupont de Nemour, Canada), "Marlex" (Phillips), "Neozex" and "Ultzex"
(Mitsui Petrochemical Industries), "Nisseki Linirex" (Nippon
Petrochemicals), "Stamilex" (DSM) "Mitsubishi Polyethy-LL" (Mitsubishi
Petrochemical), and the like. Preferable L-LDPE resins in view of physical
strength, heat seal strength and film moldability are copolymers of
ethylene and .alpha.-olefin, of which the number of carbon atoms is 6 to
8, having a melt flow rate (MFR) of 0.8 to 10 g/10 minutes (ASTM D-1238)
and a density of 0.870 to 0.940 g/cm.sup.3 (ASTM D-1505) manufactured by
the liquid slurry process or the vapor process. In the case of injection
molding, particularly, preferable L-LDPE resin in view of the lealance
between the improvement in physical strength and injection moldability are
those having a MI of 2-80 g/10 minutes, a density of 0.890-0.980
g/cm.sup.3, preferably 0.900 to 0.970 g/cm.sup.3, using an .alpha.-olefin
having a number of carbon atoms of 3-8 manufactured by the liquid slurry
process or the vapor process. Very low density L-LDPE resins having a
density of less than 0.910 g/cm.sup.3 are also preferred, particularly for
the surface layer because film rupture, film cracks or pinholes do not
occur, even if the layer is thinned with increase in the light-shielding
material content.
In the molded article of the invention, it is preferable to blend various
known thermoplastic elastomers in an amount of not less than 3 wt. %,
preferably 6 to 50 wt. %, particularly preferably 10 to 40 wt. %, for the
purpose of the improvement in flexibility, impact strength at low
temperature or the like. A particularly preferable thermoplastic elastomer
is ethylene-propylene rubber, and as the ethylene-propylene rubber, there
are two kinds, i.e. EPM which a copolymer of ethylene and propylene and
EPDM which is a ternary copolymer of ethylene, propylene and diene monomer
for crosslinking, such as ethylidene norbornene. Since EPM and EPDM do not
contain unsaturated bond in their polymer main chain, they are excellent
in heat resistance and weather resistance and do not adversely affect
photographic photosensitive materials, and therefore particularly
preferred.
To the resin film for photographic photosensitive materials which is one of
the molded articles of the invention, it is preferable to blend
antiblocking agent in order to prevent blocking. As the antiblocking
agent, there are silica including natural silica and synthetic silica,
calcium carbonate, talc (magnesium silicate), aluminum silicate, calcium
silicate, fatty acid amide lubricant, higher fatty acid polyvinyl ester,
n-octadecylurea, N,N'-dioleyloxamide, N-ethanolstearic amide, dicarboxylic
acid ester amide, etc., and silica is preferred. A suitable blending
amount is 0.01 to 5 wt. %. When the blending amount is less than 0.01 wt.
%, antiblocking effect is insufficient. When the blending amount exceeds 5
wt. %, not only lump-formed unevenness trouble occurs, but also physical
strength and heat sealing properties of the resin film degrade. Preferable
silica has a mean particle size of 0.3 to 20 .mu.m. When the mean particle
size is less than 0.3 .mu.m, aggregation is liable to occur to generate
lumps frequently, and antiblocking effect is small. When the mean particle
size is more than 20 .mu.m, the film surface is rough by exposing silica
particles, and abrasion is liable to occur on the surface of photographic
photosensitive materials.
The lubricant includes fatty acid amide lubricants, unsaturated fatty acid
amide lubricants, bis fatty acid amide lubricants, monoalkyl amide
lubricants, silicone lubricants, nonionic surfactant lubricants,
hydrocarbon lubricants, fatty acid lubricants, ester lubricants, alcohol
lubricants, metallic soap lubricants, etc. Examples of the lubricant are
as follows:
Saturated fatty acid amide lubricants
Behenic acid amide lubricants: "DIAMID KN" (Nippon Kasei Chemical Co.,
Ltd.)
Stearic acid amide lubricants: "ARMIDE HT" (Lion), "ALFLOW S-10" (Nippon
Oil and Fats Co., Ltd.), "FATTY AMIDE S" (Kao Corp.), "NEWTRON 2" (Nippon
Fine Chemical Co., Ltd.), "DIAMID 200" and "DIAMID AP-1" (Nippon Kasei
Chemical Co., Ltd.), "AMIDE S" and "AMIDE T" (Nitto Kagaku K. K.), etc.
Hydroxystearic acid amide lubricants
Palmitic acid amide lubricants: "NEWTRON S-18" (Nippon Fine Chemical Co.,
Ltd.), "AMIDE P" (Nitto Kagaku K. K.), etc.
Lauric acid amide lubricants: "ARMIDE C" (Lion Akzo Co., Ltd.), "DIAMID"
(Nippon Kasei Chemical Co., Ltd.), etc.
Unsaturated fatty acid amide lubricants
Erucic acid amide lubricants: "ALFLOW P-10" (Nippon Oil and Fats Co.,
Ltd.), "NEWTRON-S" (Nippon Fine Chemical Lo., Ltd.), "LUBROL" (I.C.I.),
"DIAMID L-200" (Nippon Kasei Chemical Co., Ltd.), etc.
Oleic amide lubricants: "ARMOSLIP-CP" (Lion Akzo Co., Ltd.), "NEWTRON" and
"NEWTRON E-18" (Nippon Fine Chemical Co., Ltd.), "AMIDE-0" (Nitto Kagaku
K. K.), "DIAMID O-200" and "DIAMID G-200" (Nippon Kasei Chemical Co.,
Ltd.), "ALFLOW E-10" (Nippon Oil and Fats Co., Ltd.), "FATTY AMIDE 0" (Kao
Corp.), etc.
Bis fatty acid amide lubricants
Methylene bis behenic acid amide lubricants: "DIAMID NK BIS" (Nippon Kasei
Chemical Co., Ltd.), etc.
Methylene bis stearic acid amide lubricants: "DIAMID 200 BIS" (Nippon Kasei
Chemical Co., Ltd.), "ARMOWAX" (Lion Akzo Co., Ltd.), "BISAMIDE" (Nitto
Kagaku K. K.), etc.
Methylene bis oleic acid amide lubricants: "LUBRON 0" (Nippon Kasei
Chemical Co., Ltd.), etc.
Ethylene bis stearic acid amide lubricants: "ARMOSLIP EBS" (Lion Akzo Co.,
Ltd.), etc.
Hexamethylene bis stearic acid amide lubricants: "AMIDE 65" (Kawaken Fine
Chemicals Co., Ltd.), etc.
Hexamethylene bis oleic acid amide lubricants: "AMIDE 60" (Kawaken Fine
Chemicals Co., Ltd.), etc.
Nonionic surfactant lubricants: "ELECTROSTRIPPER TS-2" , "ELECTROSTRIPPER
TS-3" (Kao Corp.), etc.
Hydrocarbon lubricants: liquid paraffin, natural paraffin, microwax,
synthetic paraffin, polyethylene wax (preferably not more than 6,000 of
weight average molecular weight), polypropylene wax (preferably not more
than 6,000 of weight average molecular weight), chlorinated hydrocarbon,
fluorocarbon, etc.
Fatty acid lubricants: higher fatty acids preferably more than C.sub.12,
such as caproic acid, stearic acid, oleic acid, erucic acid and palmitic
acid, hydroxy fatty acids, etc.
Ester lubricants: fatty acid lower alcohol esters, fatty acid polyol
esters, fatty acid polyglycol esters, fatty acid fatty alcohol esters,
etc.
Alcohol lubricants: polyols, polyglycols, polyglycerols, etc.
Metallic soap: metal salts, such as Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cd, Al,
Sn, Pb salts, of higher fatty acids, such as lauric acid, stearic acid,
succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic
acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid,
palmitic acid, erucic acid, etc., and magnesium stearate, calcium
stearate, zinc stearate, magnesium oleate are preferable.
Partially saponified montanic acid esters
Silicone lubricants: dimethylpolysiloxanes, modified thereon, in various
grades (Shin-Etsu Silicone, Troay Silicone). Various silicone oils are
preferable because of exhibiting an expected effects, such as the
improvement in the dispersibility of coloring material, the improvement in
coloring power and light-shielding due to the increase of haze by making
resin turbid into white and the like, as well as the improvement in resin
fluidity, slipping character, etc.
The above silicone oil has preferably a viscosity at ordinary temperature
of 50 to 100,000 centistockes, more preferably 5,000 to 30,000
centistockes. Suitable silicone oils are those having modified siloxane
bond, such as polydimethylsiloxane, polymethylphenylsiloxane,
olefin-modified silicone, amide-modified silicone, amino-modified
silicone, carboxyl-modified silicone, .alpha.-methylstyrene-modified
silicone, polyether-modified silicone modified with polyethylene glycol,
polypropylene glycol, etc., olefin/polyether-modified silicone,
epoxy-modified silicone, alcohol-modified silicone, etc. Among them,
olefin-modified silicone, polyether-modified silicone and
olefin/polyether-modified silicone are preferable. The silicone oil
improves friction coefficient of molded articles, such as film, in a
heated condition, decreases sliding resistance generated during hot plate
sealing in an automatic packaging machine and prevents the occurrence of
wrinkling. Thereby, the silicone oil provides a basis of producing a film
which has a beautiful appearance, a high sealability, and adhesion to an
article to be packaged without sagging. It prevent the degradation of
gloss by sliding to form a fine sealed portion. In the case of using
silicone oil, friction coefficient at high temperature can be not more
than 1.4 for sliding heat seal.
Effects of blending silicone oil are, when fiber filler, nonfiber
light-shielding material or pigment is blended together, the silicone oil
coates their surface to improve their dispersibility. Silicone oil
improves the dispersibility of resin, decrease motor load of screw and
prevents the occurrence of melt fracture. Slipping character can be
ensured sufficiently without blending fatty acid amide which tends to
bleed out to generate white powder. A fine sealed portion can be formed by
decreasing the friction coefficient of a molded article in heated
conditions, improving automatic bag-making ability, and preventing the
occurrence of wrinkling at the time of heat sealing and the reduction o
gloss by sliding. When light-shielding material is combined, coloring
force and light-shielding ability can be improved by making thermoplastic
resin turbid into white to increase haze. As a result, light-shielding
ability can be ensured, even though the blending amount of light-shielding
material which degrades properties is decreased.
A suitable content of the lubricant varies according to the kind. Among the
lubricants the most suitable for the molded article of the invention, in
the case of the lubricants having a small lubricating ability used for
keeping photographic properties as the main object, such as metal salts of
fatty acids, a suitable content is 0.03 to 5 wt. %, preferably 0.05 to 3
wt. %, particularly preferably 0.1 to 1.5 wt. %. In the case of the
lubricants having a great lubricating ability, being liable to bleed out
and affecting photosensitive materials, such as fatty acid amide lubricant
and bis fatty acid amide lubricant, a suitable content is 0.01 to 1 wt. %,
preferably 0.03 to 0.5 wt. %, particularly preferably 0.05 to 0.3 wt. %.
Antistatic agent applicable to the invention includes:
Nonionic Antistatic Agent:
Alkylamine derivatives:
Polyoxyethylene alkyl amine, tertiary amine e.g. laurylamine,
N,N-bis(2-hydroxyethyl cocoamine, N-hydroxyhexadecyl-di-ethanolamine,
N-hydroxyoctadecyl-di-ethanolamine, etc.
Fatty acid amide derivatives:
Oxalic acid-N,N'-distearylamide butyl ester, polyoxyethylene alkyl amide,
etc.
Ethers:
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, etc.
Polyol esters:
Glycerine fatty acid esters, sorbitan fatty acid esters,
1-hydroxyethyl-2-dodecylglyoxazoline, etc.
Anionic Antistatic Agent:
Sulfonates:
Alkyl fulfonate (RSO.sub.3 Na), alkylbenzene sulfonate, alkyl sulfate
(ROSO.sub.3 Na), etc.
Phosphate esters:
Alkyl phosphate, etc.
Cationic Antistatic Agent:
Cationic amides:
Quaternary ammonium salts:
Quaternary ammonium chloride, quaternary ammonium ammonium sulfate,
quaternary ammonium nitrate, e.g. stearamide
propyl-dimethyl-.beta.-hydroxyethyl ammonium nitrate, etc.
Ampholytic Antistatic Agent:
Alkyl betaines:
Imidaxolines:
Alkyl imidazolines:
Metal salts:
(RNR'CH.sub.2 CH.sub.2 CH.sub.2 NCH.sub.2 COO).sub.2 Mg {R.gtoreq.C, R'=H
or (CH.sub.2).sub.m COO--,}etc.
Alkyl alanines:
Conductive resin:
Polyvinylbenzyl cation, polyacrylic acid cation, etc.
Among them, nonionic antistatic agents are particularly preferred, because
adverse affect upon photographic properties and human body is small.
A suitable blending amount of the antistatic agent is 0.01 to 5 parts by
weight, preferably 0.05 to 3 parts by weight, particularly preferably 0.1
to 1.5 parts by weight per 100 parts by weight of the crystalline resin
composition. When the blending amount is less than 0.01 part by weight,
the blending effect is insufficient. When the blending amount exceeds 5
parts by weight, slip between the screw of an extruder and a molten resin
is liable to occur resulting in the variation of the ejected resin amount.
Greasiness and bleeding out with time are also liable to occur.
A dripproofing substance is incorporated in the molded article for
photographic photosensitive materials in order to prevent adhesion of dew
and to inhibit the deposition of additives liable to bleed out to form
white powder, such as lubricant and antioxidant.
As the dripproofing substance, there are water-absorptive or hygroscopic
substance and dripproofing agent, and includes any substance which renders
a contact angle of water of less than 45 degrees, preferably less than 35
degrees.
The dripproofing agent includes diglycerine monostearate ester,
polyglycerine monopalmitate ester, sorbitan monolaurate ester, sorbitan
monoerucate, polyoxyethylene sorbitan fatty acid ester, stearic acid
monoglyceride, palmitate monoglyceride, oleate monoglyceride, laurate
monoglyceride, polyoxyethylene nonylphenyl ether, sorbitan
sesquipalmitate, diglycerine sesquioleate, sorbitol fatty acid ester,
sorbitol fatty acid dibasic acid ester, diglycerine fatty acid dibasic
acid ester, glycerine fatty acid dibasic acid ester, sorbitan fatty acid
dibasic acid ester, sorbitan palmitate, sorbitan stearate, sorbitan
palmitate propylene oxide 3 moles adduct, sorbitan palmitate propylene
oxide 2 moles adduct, sorbitol stearate, sorbitol stearate ethylene oxide
3 moles adduct, diglycerine palmitate, glycerine palmitate, glycerine
palmitate ethylene oxide 2 moles adduct, etc.
The dripproofing agent, the water-absorptive substance and the hygroscopic
substance may be combined.
It is preferable to provide the molded article for photographic
photosensitive materials containing the dripproofing substance with a
surface activation treatment, such as corona discharge, ozone treatment or
plasma treatment because of exhibiting dripproof action and antifog action
more effectively.
A suitable blending amount of the dripproofing substance is 0.01 to 5 wt.
%, preferably 0.1 to 3 wt. %. When the blending amount is less than 0.01
wt. %, antifog effect is insufficient. The effect of inhibiting the
deposition in a form of white powder of additives liable to bleed out,
such as lubricant and antioxidant is also insufficient. When the blending
amount exceeds 5 wt. %, although the antifog effect is sufficiently
exercised, the effect increased by increasing the blending amount is
little. Moreover, the surface of the molded article becomes greasiness,
and dust is liable to adhere. When dust adheres on a photographic film,
uneven developing rate trouble occurs.
The crystalline resin composition is composed of the aforementioned
crystalline resin, lubricant and antistatic agent, and the blending amount
of various additives described later is set based on 100 parts by weight
of the crystalline resin composition.
Antioxidant is blended in the molded article for photographic
photosensitive materials of the invention. Oxidative degradation tends to
occur in polyolefin resin having more CH.sub.3 branches due to a greater
oxygen absorption. Accordingly, oxidative degradation occurs in the order
to more: polypropylene resin>homopolyethylene
resin>ethylene-.alpha.-olefin copolymer resin: less. Various polyethylene
resins (containing ethylene-.alpha.-olefin copolymer resins) and various
polypropylene resins (containing propylene-ethylene random copolymer
resins) being representative crystalline thermoplastic resins are
hydrocarbons, and it is considered that when a radical group is produced
through dehydration of hydrocarbon in the presence of oxygen, antoxidation
proceeds in the following formulas as chain reaction.
RH.fwdarw.Re.
R.+0.sub.2 .fwdarw.ROO.
ROO.+RH.fwdarw.ROOH+R.
ROOH.fwdarw.RO.+.OH
RO.+RH.fwdarw.ROH+R.
.OH+RH.fwdarw.HOH+R.
Thus, the oxidation of hydrocarbon is accelerated to produce a great
quantity of alcohols, aldehydes, acids and the like, and they react with
each other to produce polymer. In order to prevent oxidation of
hydrocarbon, it is necessary to intercept the above chain reaction, and
antioxidant is used for that purpose. Besides, it is also preferable to
add the following radical scavenger.
As the radical scavenger suitable for the invention, there are
1,1-diphenyl-2-picrylhydrazyl, 1.3.5-triphenylferudazyl,
2.2,6.6-tetramethyl-4-piperidone-1-oxyl, N-(3-N-oxyanilino-1
3-dimethylbytylidene)anilinoxide, high valency metal salts, such as ferric
chloride, diphenylpicrylhydrazine, diphenyamine, hydroquinone,
t-butylcatechol, dithiobenzyldisulfide, p.p'-ditolyltrisulfide,
benzoquinone derivatives, nitro compounds, nitroso compounds, and the
like. Among them, to use hydroquinone is particularly preferred. The above
radical scavenger may be used as a single material, or several kinds may
be combined. A suitable content of the radical scavenger is 1,000 to
10,000 ppm.
It is particularly preferable to combine phosphoric acid, phosphoric acid
compound, citric acid, citric acid compound or the like with at least one
of the above antioxidants or radical scavengers because of improving the
oxidation inhibition synergistically. A suitable content of the
antioxidant synerist (the phosphoric acid, etc.) is 0.001 to 2 wt. %,
preferably 0.005 to 1.5 wt. %, particularly preferably 0.01 to 1 wt. %.
As the antioxidant, there are radical group chain terminator which reacts
with radical groups, mainly ROO which are chain carriers, to inactivate
them, and peroxide decomposer which decomposes hydroperoxide ROOH which is
the main source of radical groups, to stabilize it. The radical group
chain terminator includes alkylphenol antioxidant and aromatic amine
antioxidant. The peroxide decomposer includes sulfur-containing
antioxidant and phosphorus-containing antioxidant. It is preferable to
combine the radical group chain terminator and the peroxide decomposer, in
order to prevent resin yellowing or browning or the generation of lumps
caused by the thermal degradation of thermoplastic resin. Since
antioxidant is a reducing agent which adversely affects photographic
photosensitive materials, unless its kind and the blending amount is
carefully examined, degradation of photographic photosensitive materials
becomes a great problem.
In order to prevent thermal degradation of thermoplastic resin,
particularly polyolefin resin, it is preferable to blend 0.001 to 1 wt. %,
preferably 0.005 to 0.8 wt. %, particularly preferably 0.01 to 0.5 wt. %
of organic cyclic phosphorus compound as a single material or combined
with other antioxidant. As the antioxidant combined therewith, it is
preferable to blend 0.001 to 1 wt. %, preferably 0.005 to 0.8 wt. %,
particularly preferably 0.01 to 0.5 wt., of phenolic antioxidant,
particularly hindered phenolic antioxidant, which has radical group chain
terminating action different from the peroxide decomposition action of the
cyclic phosphorus compound and rarely affects adversely photographic
photosensitive materials. It is also preferable further to blend
aforementioned radical scavenger and/or phosphoric acid, citric acid, etc.
in addition to the above combination because longer continuous molding
becomes possible.
Examples of suitable organic cyclic phosphorus compounds are as follows:
##STR1##
In the formula, R.sub.1 represents tertiary butyl group or tertiary amyl
group, R.sub.2 represents alkyl group having a number of carbon atoms of
1-9, R.sub.3 represents hydrogen atom or alkyl group atom or alkyl group
having a number of carbon atoms of 1-4, and R.sub.4 represents alkyl group
having a number of carbon atoms of 1-30 or aryl group having a number of
carbon atoms of 6-15.
##STR2##
In the formula, the definition of R.sub.2, R.sub.3 and R.sub.4 is the same
as above.
##STR3##
In the formula, the definition of R.sub.2 and R.sub.3 is the same as above.
M represents alkali metal atom.
##STR4##
In the above formula, the definition of R.sub.3 is the same as above,
R.sub.5 and R.sub.6 represent hydrogen atom, alkyl group, cycloalkyl
group, aryl group or alkyl group having a number of carbon atoms of 1-12,
and X represents --OH group or --O.sup.- NH.sub.4.sup.+.
In order to prevent photodegradation of the container for a photographic
film, it is preferable to add 0.001 to 5 wt. %, preferably 0.005 to 3 wt.
%, particularly preferably 0.01 to 1 wt. %, of ultraviolet absorber.
Particularly preferable ultraviolet absorbers are hindered amine
ultraviolet absorbers, such as 2.2,6.6-tetramethyl-4-piperidinol,
2.2,6.6-tetramethyl-4-piperidylbenzoate, etc., and benzophenone salicylic
acid compounds, benzotrizaole compounds, ultraviolet absorbers.
Examples of the antioxidant are as follows:
Phenol Antioxidants:
vitamin E (.alpha.-tocopherol), 6-t-butyl-3-methylphenol derivatives,
2,6-di-t-butyl-phenol, 2,6-di-t-butyl-p-ethylphenol,
2,6-di-t-butyl-p-cresol (BHT),
2,2'-methylenebis-(4-ethyl-6-t-butylphenol), 2,2-methylenebis-(4-methyl-6-
t-butyl-phenol), 4,4'-butylidenebis(6-t-butyl-m-cresol),
4,4'-thiobis(6-t-butyl-m-cresol), 4,4-dihydroxydiphenylcyclohexane, alkyl
group-induced bisphenol, styrene group-induced phenol,
2,6-di-t-butyl-4-methylphenol,
n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate,
2,2'-methylenebis(4-methyl-6-t-butylphenol),
4,4'-butylidenebis(3-methyl-6-t-butylphenol),
stearyl-.beta.-(3,5-di-4-butyl-4-hydroxyphenyl)propionate,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
tetrakis [methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl) propionate]
methane, etc.
Ketone-Amine Condensae Antioxidants:
6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, polymers of
2,2,4-trimethyl-1,2-dihydroquinoline, trimethyldihydroquinoline
derivatives, etc.
Arylamine Antioxidants:
Phenyl-.alpha.-naphthylamine, N-phenyl-.beta.-naphthylamine,
N-phenyl-N'-isopropyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine, N,N'-di-.beta.-naphthyl-p-phenylenediami
ne, N-(3'-hydroxybutylidene)-1-naphtylamine, etc.
Imidazole Antioxidants:
2-mercaptobenzoimidazole, zinc salt of
2-mercaptobenzoimidazole,
2-mercaptomethylbenzoimidazole, etc.
Phosphite Antioxidants:
Alkyl-induced arylphosphite, diphenylisodecylphosphite, sodium phosphite
salt of tris(nonylphenyl)phosphite, trinonylphenylphosphite,
triphenylphosphite, etc.
Thiourea Antioxidants:
Thiourea derivatives, 1,3-bis(dimethylaminopropyl)-2-thiourea, etc.
Other Antioxidants:
Those useful for air oxidation, such as dilauryl thiodipropionate, metal
deactivators, etc.
Preferable antioxidants are phenol antioxidants, and particularly effective
antioxidants are BHT, low volatile high molecular weight phenol
antioxidants ("Irganox 1010", "Irganox 1076", trade names of Ciba-Geigy A.
G., "Ionox 330", trade name of Shell, "Good-Rite 3114" trade name of
Good-rich, "Topanol C A", trade name of I. C. I., etc.),
dilaurylthiodipropionate, distearylthiodipropionate, dialkylphosphate,
etc. Two or more antioxidants may be combined.
Particularly preferable antioxidants are hindered phenolic antioxidants
because of rare adverse affect upon photographic properties of
photographic photosensitive materials. The hindered phenolic antioxidants
are 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene,
tetrakis [methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)methane],
octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 2,2',2'-tris
(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy ethylisocyanulate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) isocyanulate,
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite ester,
tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]
methane, 4,4'-triobis-(6-tert-butyl-o-cresol),
2,2'-thiobis-(6-tert-butyl-4-methylphenol),
tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
2,2'-methylene-bis-(4-methyl-6-tert-butylphenol),
4,4'-methylene-bis-(2,6-di-tert-butylphenol),
4,4'-butylidenebis-(3-methyl-6-tert-butylphenol),
2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol,
2,6-di-tert-4-n-butylphenol,
2,6-bis(2'-hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-methylphenol,
4,4'-methylene-bis-(6-tert-butyl-o-cresol),
4,4'-butylidene-bis-(6-tert-butyl-m-cresol) and the like. According to the
properties of antioxidants, two or more kinds of antioxidants may be
combined. Preferable antioxidants have a melting point of more than
100.degree. C., particularly preferably more than 120.degree. C.
It is preferable to combine at least one kind of a hindered phenolic
antioxidants having a melting point of more than 100.degree. C.,
preferably more than 120.degree. C. which is a representative radical
group chain terminator and at least one kind of phosphorus-containing
antioxidants, because of enhancing the effect of inhibiting thermal
degradation of resins and additives without degrading photographic
properties.
Besides, other antioxidants usable in the invention can be selected from
those disclosed in "Plastic Data Handbook" (published by Kygyo Chosa Kai),
pages 794-799, "Plastic Additives Data Collection" (published by Kagaku
Kogyo), pages 327-329, "Plastic Age Encyclopedia, Advance Editions 1986"
(published by Plastic Age), pages 211-212, etc.
A suitable blending amount of the antioxidant is 0.0005 to 2 parts by
weight, preferably 0.001 to 1 part by weight, particularly preferably
0.005 to 0.45 part by weight per 100 parts by weight of the crystalline
resin composition. As the content of the antioxidant in the molded
article, 0.0008 to 0.8 wt. % is preferable, and 0.0015 to 0.4 wt. % is
particularly preferred.
The acrylic acid copolymer resin includes various ethylene copolymer
resins, such as ethylene-acrylic acid copolymer resin, ethylene-methyl
acrylate copolymer resin, ethylene-ethyl acrylate copolymer resin,
ethylene-butyl acrylate copolymer resin, ethylene-2-ethylhexyl acrylate
copolymer resin, ethylene-methacrylate copolymer resin, ethylene-methyl
methacrylate copolymer resin, ethylene-ethyl methacrylate copolymer resin
and ethylene-butyl methacrylate copolymer resin, and various styrene
copolymer resins, such as styrene-methyl acrylate copolymer resin,
styrene-ethyl acrylate copolymer resin, styrene-propyl acrylate copolymer
resin, styrene-butyl acrylate copolymer resin and styrene-2-ethylhexyl
acrylate copolymer resin. Particularly suitable resin is ethylene-ethyl
acrylate copolymer (EEA) resin having a MFR of 1 to 250 g/10 minutes,
preferably 2 to 50 g/10 minutes, particularly preferably 3 to 30 g/10
minutes and an ethyl acrylate content of 3 to 50 wt. %, preferably 5 to 40
wt. %, particularly preferably 7 to 25 wt. %.
A suitable blending amount of the acrylic acid copolymer is 5 to 90 parts
by weight, preferably 10 to 80 parts by weight, particularly preferably 15
to 70 parts by weight, per 100 parts by weight of the crystalline resin
composition. As the content of the acrylic acid copolymer in the molded
article, 8 to 70 wt. % is preferable, and 12 to 60 wt. %, is more
preferred.
When light-shielding ability is imparted to the molded article for
photographic photosensitive materials of the invention, light-shielding
material may be blended.
Representative examples of the light-shielding material is shown below.
Inorganic Compounds
Oxides . . . Silica, diatomaceous earth, alumina, titanium oxide, iron
oxide, zinc oxide, magnesium oxide, antimony oxide, barium ferrite,
strontium ferrite, berylium oxide, pumice, pumice balloon, alumina fiber,
etc.
Hydroxides . . . aluminum hydroxides, magnesium hydroxides, basic magnesium
carbonate, etc.
Carbonates . . . calcium carbonate, magnesium carbonate, dolomite,
dawsonite, etc.
Sulfates, sulfites . . . calcium sulfate, barium sulfate, ammonium sulfate,
calcium sulfite, etc.
Silicates . . . talc, clay, mica, asbestos, glass fiber, glass balloon,
glass bead, calcium silicate, montomorillonite, bentonite, zeolite, etc.
Carbons . . . carbon black, graphite, carbon fiber, carbon hollow bead,
etc.
Others . . . iron powder, copper powder, lead powder, tin powder, stainless
steel powder, pearl pigment, aluminum powder, molybdenum sulfide, boron
fiber, silicon carbide fiber, brass fiber, potassium titanate, lead
titanate zirconate, zinc borate, barium metaborate, calcium borate, sodium
borate, aluminum paste, etc.
Organic Compounds: wood flour such as pine, oak and sawdust, husk fiber
such as almond, peanut and chaff, colored various fibers such as cotton,
jute, paper piece, cellophane piece, nylon fiber, polypropylene fiber,
various starch (containing modified starch, surface-treated starch, etc.),
aromatic polyamide fiber, etc.
Among them, carbon black is preferable because of decreasing the bleeding
out of lubriant, surfactant and the like. Carbon blacks are divided into
gas black, oil furnace black, channel black, anthracene black, acetylene
black, Ketchen carbon black, thermal black, lamp black, vegetable black
and animal black according to their origin. Among these, oil furnace
carbon black is preferable in terms of photographic properties,
light-shielding character, cost and improvement of properties. On the
other hand, since acetylene black and Ketschen carbon black which is
modified by-produced carbon black have an antistatic character, they are
also preferable, though they are expensive. They may be blended to the oil
furnace black in order to improve its character. Although, there are
various blending method, such as dry coloring, liquid coloring, paste
color, masterbatch pellets, compound color pellets and granular color
pellets, the masterbatch method using masterbatch pellets is preferred in
view of cost and less contamination of the working place. Japanese Patent
KOKOKU No. 40-26196 discloses a method of making a masterbatch of
polymer-carbon black by dissolving the polymer in an organic solvent and
dispersing the carbon black into the solution. Japanese Patent KOKOKU NO.
43-10362 discloses another method of making a masterbatch by dispersing
the carbon black into polyethylene.
Particularly preferable carbon black for the molded article for
photographic photosensitive materials is the oil furnace carbon black
having a pH (JIS K 6221) of 6 to 9, preferably pH 6.5 to 8.5, a mean
particle size measured by microscopy of 10 to 120 .mu.m, preferably 12 to
70 .mu.m, a volatile components content (JIS K 6221) of less than 3.5%,
preferably less than 1.5%, and a DBP oil absorption value (JIS K 6221) of
more than 50 ml/100 g, preferably more than 70 mg/100 g, in view of no
occurrence of fogging, rare occurrence of photosensitivity deviation and
great light-shielding ability. Moreover, when it is blended in polyolefin
resin injection molded articles, polystyrene resin injection molded
articles, L-LDPE resin films or the like, the lumps of carbon black and
fish eyes rarely occur. Channel black is not preferred because of
containing components inducing fogging, such as sulfur component, in
quantity and volatile components of frequently exceeding 5%, as well as
expensiveness. Lamp black is also not preferable because of having a pH of
less than 5 adversely affecting photographic properties. Unless sulfur
components of carbon black is less than 0.9%, preferably less than 0.7%,
measured by ASTM D-1619-60, photographic properties are adversely
affected. Since free sulfur components are particularly adversely affect
photographic properties, it is preferable to select carbon black
containing free sulfur components of less than 0.1%, preferably less than
0.05%.
As the preferable light-shielding materials, inorganic pigments having a
refraction index measured by the Larsen oil immersion method of more than
1.50, various metal powders, metal flakes, metal pastes, metal fibers, and
carbon fiber are next to carbon black. Representative examples are
titanium oxide in rutile type (2.76), titanium oxide in anatase type
(2.52), zinc oxide (2.37), antimony oxide (2.35), lead white (2.09), zinc
white (2.02), lithopone (1.84), baryta powder (1.64), barium sulfate
(1.64), calcium carbonate (1.58), talc (1.58), calcium sulfate (1.56),
silicic anhydride (1.55), silica powder (1.54), magnesium hydroxide
(1.54), basic magnesium carbonate (1.52), alumina (1.50), and the like.
The number in parenthesis indicates refraction index. Particularly
preferable light-shielding materials are inorganic pigments having a
refraction index of not less than 1.56, more preferably not less than
1.60. On the other hand, since calcium silicate (1.46), diatomaseous earth
(1.45), hydrous silicate (1.44) and the like have a refraction index of
less than 1.50, they are unsuitable.
Recently, X-ray checking apparatus is used for baggage inspection at air
port. When a high sensitivity photographic film having a sensitivity of
ISO photographic speed 400 or more is passed through the X-ray checking
apparatus, fogging is liable to occur on the photographic film by X-ray.
To blend a light-shielding material having a specific gravity of not less
than 3.4 is preferable for preventing the occurrence of fogging by the
X-ray.
The light-shielding material having X-ray-shielding ability as well as
light-shielding ability has a specific gravity of not less than 3.4,
preferably not less than 4.0, and the form may be any form, such as
pigment, powder, flake, whisker or fiber. Examples of the light-shielding
material having X-ray-shielding ability are barium sulfate, molybdenum
disulfide, lead oxide (lead white), iron oxide, magnesium oxide, barium
titanate, copper powder, iron powder, silver powder, lead powder, steel
powder, zinc powder, tungsten whisker, silicon nitride whisker, copper
whisker, iron whisker, nickel whisker, chromium whisker, stainless steel
powder and whisker, antimony trioxide, barium carbonate, zinc white,
chromium oxide, tin powder, their mixtures, etc. Particularly preferable
ones are barium sulfate, barium chloride, barium titanate, lead powder,
lead oxide, zinc powder, zinc white, tin powder, stainless steel powder,
stainless steel whisker, iron oxide, tungsten whisker, nickel whisker,
etc. A suitable content of the X-ray-shielding light-shielding material is
5 to 80 wt. %, preferably 10 to 70 wt. %, particularly preferably 20 to 60
wt. %. In order not to affect adversely photographic photosensitive
materials and not to degrade film moldability, the X-ray-shielding
light-shielding material is used preferably in a state that weight loss or
drying at 100.degree. C. for 5 hours is not more than 2 wt. %, preferably
not more than 1 wt. %, particularly preferably not more than 0.5 wt.
As oil-absorptive inorganic pigment having a function of adsorbing
lubricant, antioxidant and organic nucleating agent, which are liable to
bleed out, deodorant, agent for adding fragrance, oxygen scavenger, etc.,
there are zinc white (50), asbestine (50), clay (51), talc (60), carbon
black (not less than 50) and the like.
The metal powder includes metal paste, and examples are copper powder,
stainless steel powder, iron powder, silver powder, tin powder, zinc
powder, steel powder and the like.
As the aluminum powder including aluminum paste, aluminum powder of which
the surface is coated with a surface-coating material and aluminum paste
from which low volatile components are removed and then kneaded with a
thermoplastic resin are preferred. The paste of aluminum powder is
produced by adding a liquid medium such as mineral spirits or and a small
amount of a higher fatty acid such as stearic acid or oleic acid to form a
paste at the production of aluminum powder according to a known method
such as using a ball mill, a stamp mill or an atomizer. The aluminum paste
is kneaded together with an aromatic monovinyl resin, such as polystyrene
resin or rubber-containing polystyrene resin, a polyolefin thermoplastic
resin, such as various polypropylene resins, various polyethylene resins,
acid-modified resins, EVA resin, EEA resin or EAA resin, low molecular
weight polyolefin resin, paraffin wax, tackifier, dispersing agent, such
as metallic soap, etc. under heat, and volatile components mainly mineral
spirits and white spirits are removed by heat, a vacuum pump or the like
up to the low volatile component of not more than 3%, preferably not more
than 1%, particularly preferably not more than 0.5%. This product is
preferably used as aluminum paste compound resin or aluminum paste
masterbatch resin. The aluminum paste masterbatch resin is preferable
because noxious odors and adverse influences upon the photographic
photosensitive materials are eliminated. In order to eliminate noxious
odor and adverse influences upon the photographic photosensitive
materials, the content of mineral spirits should be less than 0.1 wt. %.
When the aluminum paste content of the molded article is made 2 wt. % by
using a masterbatch resin containing 40 wt. % of aluminum paste and 1.0
wt. % of mineral spirits, one part by weight of the masterbatch resin is
blended with 19 parts by weight of the main resin. Since part of the
mineral spirits evaporates during molding, the final conent of the mineral
spirits is less than 0.05 wt. %. The aluminum powder includes microflakes
produced from aluminum foil which is crushed by a ball mill or a stamp
mill, in addition to typical aluminum powder manufactured by atomization,
dropping on a rotary disc or evaporation from melted aluminum. Since
aluminum powder is unstable, it is stabilized by a known treatment.
A suitable content of the light-shielding material is 0.1 to 20 wt. % in
total in order to ensure qualities as goods, photographic properties,
moldability and economical view point of the molded article for
photographic photosensitive materials of the invention, but it varies
according to light-shielding ability. In the case of carbon black and
aluminum powder excellent in light-shielding ability, a suitable content
is 0.1 to 10 wt. %, preferably 0.15 to 7 wt. %, particularly preferably
0.2 to 5 wt. % in total. When the content is less than 0.1 wt. %, unless
the thickness of the molded article is thickened, fogging occurs due to
insufficient light-shielding ability. The thickening of the molded article
results in the retardation of molding speed due to lengthening cooling
time, and the cost increases by the increase of resin. When the content
exceeds 20 wt. %, dispersibility becomes worse to generate microgrits
(lumps) which induces pressure marks and abrasion on photographic
photosensitive materials. Moreover, a water content of the molded article
increases by the increase of water adsorbed on carbon black, and adversely
affects photographic properties, such as fogging, sensitivity deviation
and abnormal coloring, upon photographic photosensitive materials.
Furthermore, moldability of the molded article is degraded to induce the
occurrence of foaming, silver streaks, pinholes short shot or the like,
and physical strength decreases.
It is preferable to coat the surface of a light-shielding material,
preferably carbon black, aluminum powder, inorganic pigment having a
refractive index of not less than 1.50, inorganic pigment having a
specific gravity of not less than 3.4 or inorganic pigment having an oil
absorption value of not less than 50 ml/100 g, by surface-coating
material, in order to improve the dispersibility into resin and the resin
fluidity, to prevent the generation of volatile substances harmful to
photographic properties, to decrease hygroscopicity, to prevent fouling of
die lip, and the like.
As the surface-coating material, there are lubricant, antioxidant, hydrous
aluminum oxide, hydrous silicon dioxide, divalent to tetravalent alcohol,
amine compound, surfactant, organic chelate compound, coupling agent,
hydrocarbon having a softening point of not more than 90.degree.C.,
silicone oil, and the like. Two or more of them may be combined.
The lubricant, antioxidant and silicone oil may be selected from the
aforementioned ones.
The hydrous silicon dioxide in natural silica and synthetic silica.
The divalent to tetravalent alcohol is ethylene glycol, propylene glycol,
1,3-dihydroxybutane, heptamethylene glycol, trimethylolethane, glycerine,
1,2,6-hexanetriol, etc.
The surfactant may be anyone of nonionic surfactant, anionic surfactant,
cationic surfactant and ampholytic surfactant.
The amine compound primary amines, such as ethanol amine, laurylamine and
butanolamine, secondary amines, such as diethanolamine and
N-methylethanolamine, tertiary amines, such as triethanolamine and
N.N-dimethyllaurylamine, and a suitable coating amount is 0.01 to 5 wt. %
against light-shielding material.
The organic chelate compound is ethylenediaminetetraacetic acid,
N-hydroxyethyl-ethylenediamine-N,N',N"-triacetic acid,
diethylenetriaminepentaacetic acid, .beta.-diketone chelate,
nitrilotriacetic acid, sodium potassium tartarate, etc.
The coupling agent is silane compound, such as vinyl trichlorosilane, vinyl
trimethoxysilane or vinyl triethoxysilane, titanate compound, such as
isopropyl-triisostearoyl titanate, etc.
The hydrocarbon having a softening point of not more than 90.degree. C. is
EVA resin, EEA resin, EMA resin or EAA resin having a comonomer content of
not less than 5 wt. %, homopolyethylene resin having a density of less
than 0.92g/cm.sup.3, ethylene-.alpha.-olefin copolymer resin having a
density of less than 0.915 g/cm.sup.3, acid-modified polyolefin resin,
polyethylene wax, polypropylene wax, cyclopentadiene resin modimodified
hydrocarbon resin, etc.
The aforementioned dripproofing agent is also usable as the surface-coating
material of the light-shielding material.
The other materials usable as the surface-coating material are organic
aluminum compounds, such as aluminum ethylate, aluminum
monoacetylacetonate, aluminum bisethylacetoacetate and aluminum
trisacetylacetonate, organosiloxanes, such as dimethylsiloxane,
diethylsiloxane, methylethylsiloxane, diphenylsiloxane,
methyphenylsiloxane, ethylphenylsiloxane, methylhydrogensiloxane,
ethylhydrogensiloxane and phenylhydrogensiloxane, acrylic acid compounds,
such as ethyleneacrylic acid copolymer, ethylene-ethyl acrylate copolymer
and ethylene-methyl acrylate copolymer, and the like.
Representative coating by the surface-coating material are as follows:
(1) Using a coupling agent:
Coated with a coupling agent containing azidosilane compound (disclosed in
Japanese Patent KOKAI No. 62-32125).
Coated with a silane coupling agent.
Coated with a titanate coupling agent.
(2) Coated by depositing silica followed by depositing by alumina.
(3) Coated with higher fatty acid metal salt, such as zinc stearate,
magnesium stearate or calcium stearate.
(4) Coated with surfactant, such as sodium stearate, potassium stearate or
hydroxyethylene dodecylamine.
(5) Coated by reacting barium sulfide aqueous solution with sulfuric acid
aqueous solution in the presence of an excess amount of barium ion to
produce barium sulfate having a mean particle size of 0.1 to 2.5 .mu.m,
adding alkaline silicic acid solution thereto to deposit barium silicate
on the surface of the barium sulfate, and depositing hydrous silica on the
surface of the barium sulfate produced by the decomposition of the barium
silicate by adding mineral acid to the slurry.
(6) Coated with a composition consisting of one or more of the oxides
selected from hydrated oxides of metal, such as titanium, aluminum,
cerium, zinc, iron, cobalt or silicon, and oxides of metal, such as
titanium, aluminum, cerium, zinc, iron, cobalt or silicon.
(7) Coated with a polymer having one or more reactive groups selected from
aziridine group, oxiazoline group and N-hydroxyalkylamide group.
(8) Coated with polyoxyalkylene amine compound.
(9) Coated with cerium iron, selected acid amion and alumina.
(10) Coated with alkoxy titanium derivative having
.alpha.-hydroxycarboxylic acid residue as substituent.
(11) Coated with polytetrafluoroethylene.
(12) Coated with polydimethylsiloxane or modified silicone.
(13) Coated with phosphate ester compound.
(14) Coated with divalent to tetravalent alcohol.
(15) Coated with olefin wax, such as polyethylene wax or polypropylene wax.
(16) Coated with hydrous aluminum oxide.
(17) Coated with silca of zinc compound consisting of zinc chloride, zinc
hydroxide, zinc oxide, zinc sulfate, zinc nitrate, zinc acetate or zinc
citrate of a combination thereof.
(18) Coated with polyhydroxy saturated hydrocarbon. Others.
A suitable coating amount is 0.001 to 5 wt. %, preferably 0.01 to 3 wt. %,
particularly preferably 0.05 to 1.5 wt. %, against light-shielding
material, such as carbon black or aluminum powder. When the coating amount
is less than 0.001 wt. %, the coating effect is insufficient. When the
coating amount exceeds 5 wt. %, bleeding out with time increases.
Moreover, screw slip occurs to vary ejected resin amount.
As a surface-coating method, a solution of the surface-coating material is
coated on the surface of the light-shielding material by immersing,
spraying or the like and then the solvent is evaporated. The
surface-coating material may be directly kneaded with the light-shielding
material, and this method is suitable, when the surface-coating material
is in a liquid or paste state, such as lubricant, surfactant, coupling
agent, antistatic agent or the like. The surface-coating material may be
kneaded in a melted state with resin and the light-shielding material, and
in the method, wetting agent, plasticizer and/or lubricant may be added.
The surface-coated light-shielding material is effective for polyvinyl
chloride (PVC) resin, vinylidene chloride-vinyl chloride copolymer (PVDC)
resin, ethylene-vinyl alcohol copolymer (EVOH) resin, high impact
polystyrene (HIPS) resin and acrylonitrile-styrene-butadiene ternary
copolymer (ABS) resin and the like, as well as the aforementioned
polyethylene resins, polypropylene resins, polyester resins, polyamide
resins, polystyrene resins, etc. The surface-coated light-shielding
material is particularly suitable for ethylene copolymer resins for film
molding, because of excellent physical strength, heat sealing properties
and the dispersibility of light-shielding material is also particularly
suitable for various polypropylene resins, polystyrene resin, high impact
polystyrene resin and ABS resin for injection molding because of excellent
rigidity and injection moldability.
The ethylene copolymer resins suitable for blending the surface-coated
light-shielding material are similar to aforementioned, and among them, in
the case of using as a film for photographic photosensitive materials.
L-LDPE resin and EEA resin are preferable because of no adverse effect on
photographic photosensitive materials, excellent film moldability and heat
sealing properties, and great bag rupture strength, impact puncture
strength and tear strength. The L-LDPE resin is similar to aforementioned.
The EEA resin is not restricted, and commercial EEA resins have, for
example, a comonomer content of 7 to 41%, a MFR of 1.5 to 1500 g/10
minutes (ASTM D-1238), a density of 0.93 to 0.95 g/cm.sup.3 (ASTM D-1505)
a brittle temperature of -40.degree. C. to less than -75.degree. C. (ASTM
D-746) and a tensile strength of 14 to 160 kg/cm.sup.2 (ASTM D-638).
In the case of blending the surface-coated light-shielding material, the
thermoplastic resin to be blended may single resin. However, it is
preferable to combine two or more resins, and particularly different in
softening point by not less than 10.degree. C. By using the thermoplastic
resins different in softening point, various effects are obtained, such as
the improvement in the dispersibility of light-shielding material, resin
fluidity, mlet adhesion, moldability and the like. Preferable combinations
are a polyolefin resin, such as L-LDPE resin, various polypropylene resin
including propylene-.alpha.-olefin copolymer resin or various
homopolyethylene resin different in density, with EVA resin, EEA resin or
EMA resin having a comonomer content of not less than 5%, various wax, EAA
resin, acid-modified polyolefin resin, tackifier resin, or the like, a
non-crystalline resin, such as various polyethylene resin or ABS resin,
with EVA resin, EEA resin or EMA resin having a comonomer content of not
less than 7%, various low molecular weight polyolefin resin, various wax,
EAA resin, acid-modified polyolefin resin, tackifier resin, various
elastomer or the like, etc. It is also preferable to blend other
thermoplastic resins, various rubbers, various additives, various
elastomers, various modifiers, and the like, in order to adjust various
properties.
There are various molding methods using an extruder kneading molten resin
with ensuring a high physical strength, such as injection molding
described later, and various countermeasures are taken against various
problems occurring therein. For example, there are the method of improving
resin fluidity by raising resin temperature, the method of using a die
having multispiral structure. However, the former method has various
problems, such as thermal degradation of resin, the generation of lumps
and coloring troubles. The latter method has problems that the applicable
resins are limited because of special apparatus, that in the case of
L-LDPE resin, etc., heat generation and decrease of ejected resin amount
occur, that the equipment cost is high to increase the manufacturing cost
of products, etc.
The above problems can be resolved by blending 0.001 to 5 wt. %, preferably
0.005 to 3 wt. %, more preferably 0.01 to 1 wt. %, particularly preferably
0.03 to 0.5 wt. % of fatty acid amide, lower alcohol ester of fatty acid,
polyvalent alcohol ester of fatty acid, polyglycol ester of fatty acid,
various silicone oil, various coupling agent, various fatty acid metal
salt, various antistatic agent, various lubricant, various surfactant or
the like. Moreover, various improvements can be achieved, such as the
improvement in the dispersibility of light-shielding material to improve
light-shielding ability and decrease the generation of lumps, the
prevention of the degradation of photographic properties, such as the
inhibition of fogging, sensitivity deviation and fogging by friction, of
photographic photosensitive materials, the prevention of abrasion, melt
fracture, fouling of die lip, die lip streaks, wrinkling and the
generation of static marks, the improvement in moldability, and the like.
Particularly suitable additives for resolving the above problems are esters
of an aliphatic monocarboxylic acid and a monovalent aliphatic alcohol in
an amount of 0.001 to 0.5 wt. %. The ester decreases motor load, and
improves the dispersibility of light-shielding material and moldability to
render the appearance of molded articles beautiful. The ester is composed
of an aliphatic monocarboxylic acid having a number of carbon atoms of 20
to 40, preferably 25 to 35 and a monovalent aliphatic alcohol having a
number of carbon atoms of 20 to 40, preferably 25 to 35. Examples of the
aliphatic monocarboxylic acid are montanic acid, melissic acid, cerotic
acid, lacceric acid and the like. Examples of the monovalent aliphatic
alcohol are montyl alcohol, melissyl alcohol, lacceryl alcohol, ceryl
alcohol and the like. The above esters are also very excellent as the
surface-coating material of the light-shielding material because of the
improvement in the fluidity of thermoplastic resin and uniform
blendability. Moreover, when they are used for coating the surface of the
inorganic or organic nucleating agent as the dispersing agent, various
excellent effects are exercised, such as the prevention of flying away and
bleeding out, and the improvement in dispersibility and resin fluidity and
the like.
A suitable total sulfur content (ASTM D-1619) of the above composite
light-shielding material is not more than 1%, preferably not more than
0.8%, particularly preferably not more than 0.5%. A suitable free sulfur
component is not more than 150 ppm, preferably not more than 50 ppm,
particularly preferably not more than 30 ppm, and an ash content according
to ASTM D-1506 is not more than 0.5%, preferably not more than 0.4%,
particularly preferably not more than 0.3%. A suitable aldehyde compound
content is not more than 0.2%, preferably not more than 0.1%, particularly
preferably not more than 0.05%, in order to avoid advers affect upon
photographic properties. Since cyanides also adversely affect photographic
properties of photographic photosensitive materials, it is suitable that
the hydrogen cyanide quantity determined by the 4-pyridine-carboxylic acid
pyrazolone absorption photometry is not more than 20 ppm, preferably not
more than 10 ppm, particularly preferably not more than 5 ppm, converted
to the weight of carbon black.
A suitable blending amount of the light-shielding material is 0.01 to 30
wt. %, preferably 0.05 to 20 wt. %, particularly preferably 0.1 to 10 wt.
%. When a substance colored by light, such as vitamin E and photosensitive
resin, is combined, various effects are greatly exercised, such as the
improvement in coloring density, the decrease in the degradation of
physical strength, the improvement in melt sealability, in moldability and
in resin fluidity. Particularly, in the case that the thickness is not
more than 10 .mu.m, a suitable blending amount is 0.1 to 15 wt. %,
preferably 0.5 to 10 wt. %, particularly preferably 1 to 7 wt. % in view
of ensuring light-shielding and physical strength.
Fatty acid metal salt may be blended into the molded article for
photographic photosensitive materials of the invention for the purpose of
inactivating substances adversely affecting photographic properties. By
blending fatty acid metal salt, various advantages are obtained, such as
the decrease of bleeding out, the prevention from flying away of organic
nucleating agent and the improvement in the dispersibility of organic
nucleating agent. Fatty acid metal salt also improves the dispersibility
of light-shielding material and modability, and improves photographic
properties by rendering halides harmless by neutralization, which is
contained in resin and adversely affect photographic properties. As the
fatty acid metal salt, there are combination of lauric acid, stearic acid,
lactic acid, succinic acid, stearyl lactic acid, hydroxystearic acid,
ricinoleic acid, naphthenic acid, oleic acid, erucic acid or the like and
Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb or the like.
A suitable blending amount of the fatty acid metal salt is 0.01 to 10 parts
by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of
the crystalline resin composition. As the content of the fatty acid metal
salt in the molded article, a suitable content is 0.01 to 5 wt. %,
preferably 0.03 to 3 wt. %, particularly preferably 0.05 to 1.5 wt. %.
When the blending amount is 0.01 wt. %, the blending effect is
insufficient. When the blending amount exceeds 5 wt. %, bleeding out
occurs. Screw slip also occurs to vary ejected resin amount, and molding
troubles frequently occur. Unless blendability is also inferior.
The resin composition used in the invention may be blended with an organic
or inorganic nucleating agent.
The organic nucleating agent includes carboxylic acids, dicarboxylic acids,
their salts and anhydrides, salts and esters of aromatic sulfonic acids,
aromatic phosphinic acids, aromatic phosphonic acids, aromatic carboxylic
acids and their aluminum salts, metal salts of aromatic phosphoric acids,
alkyl alcohols having a number of carbon atoms of 8 to 30, condensation
products of a polyhydric alcohol and an aldehyde, and alkylamines.
Examples are aluminum p-t-butylbenzoate, 1,3-benzylidenesorbitol,
1,3,2,4-dibenzylidenesorbitol, the di-substituted benzylidene-sorbitol
represented by the following formula;
##STR5##
In the formula, R.sub.1 and R.sub.2 indicate an alkyl group or an alkoxy
group having a number of carbon atoms of 1 to 8 or a halogen, and m and n
are 0 to 3 and m+n.gtoreq.1.
metal salts, such as calcium salt and magnesium salt, of stearyl lactic
acid, the compounds, such as N-(2-hydroxyethyl)-stearylamine, represented
by the following formula;
##STR6##
In the formula, R.sub.3 indicates an alkyl group having a number of carbon
atoms of 8 to 30, and k and l are 0 to 10 and k+1.gtoreq.1.
metal salts, such as lithium salt, sodium salt, potassium salt, calcium
salt and magnesium salt, of 1,2-dihydroxystearic acid, stearyl alcohol,
lauryl alcohol, sodium benzoate, benzoic acid, and sebacic acid.
Among the organic nucleating agent, sorbitol compound is excellent in a
great crystallization-accelerating effect, rare adverse affect on
photographic properties, the decrease of molding troubles, the shortening
of molding cycle and the improvement in rigidity and in appearance.
Examples of the sorbitol compound are as follows:
di-(o-methylbenzylidene)sorbitol
o-methylbenzylidene-p-methylbenzylidene sorbitol
di-(m-methylbenzylidene)sorbitol
m-methylbenzylidene-o-methylbenzylidene sorbitol
di-(p-methylbenzylidene)sorbitol
m-methylbenzylidene-p-methylbenzylidene sorbitol
1.3-heptanylidenesorbitol
1.3,2.4-diheptanylidenesorbitol
1.3,2.4-di(3-nonyl-3-pentenylidene)sorbitol
1.3-cyclohexanecarbylidenesorbitol
1.3,2.4-dicyclohexanecarbylidenesorbitol
1.3,2.4-di(p-methylcyclohexanecarbylidene)sorbitol
Aromatic hybrocarbon groups or derivatives thereof 1.3-benzylidenesorbitol
1.3,2.4-dibenzylidene-D-sorbitol
1.3,2.4-di(m-methylbenzylidene)sorbitol
1.3,2.4-di(p-methylbenzylidene)sorbitol
1.3,2.4-di(p-hexylbenzylidene)sorbitol
1.3,2.4-di(l-naphthalenecarbylidene)sorbitol
1.3,2.4-di(phenylaceylidene)sorbitol
1.3.2.4-di(methylbenzyliden)sorbitol
1.3.2.4-di(ethylbenzylidene)sorbitol
1.3.2.4-di(propylbenzyledene)sorbitol
1.3.2.4-di(methoxybenzylidene)sorbitol
1.3.2.4-di(ethoxybenzylidene)sorbitol
1.3.2.4-di(P-methylbenzylidene)sorbitol
1.3.2.4-di(P-chlobenzylidene)sorbitol
1.3.2.4-di(P-methoxybenzylidene)sorbitol
1.3.2.4-di(alkilbenzylidene)sorbitol
1.3.2.4-di(methylbenzylidene)sorbitol
aluminumbenzoate, etc.
A suitable blending amount of organic nucleating agent is 0.005 to 5 wt. %,
preferably 0.01 to 3 wt. %, more preferably 0.03 to 2 wt. %, the most
preferably 0.05 to 1 wt. %.
Organic nucleaging agent, particularly sorbitol compounds, is vulky, having
a bulk specific gravity of 0.1.+-.0.02, and tends to fly away, and
according, it is preferable to combine a fatty acid metal salt because of
improving dispersibility, blending effect and decreasing bleeding out, as
well as preventing fly away. Preferable fatty acid metal salts have number
of carbon atoms of not less than 8. A suitable content of the fatty acid
metal salt in the molded article is 0.01 to 5 wt. %, preferably 0.03 to 3
wt. %, particularly preferably 0.05 to 1.5 wt. %. The fatty acid metal
salt also improves the dispersibility of light-shielding material and
moldability. Moreover, photographic properties are improved by rendering
halides harmless by neutralization which adversely affect photographic
properties.
In organic nucleaging agent includes an alkali metal hydroxide, such as
lithium hydroxide, sodium hydroxide and potassium hydroxide, an alkali
metal oxide, such as sodium oxide, an alkali metal carbonate, such as
lithium carbonate, sodium carbonate, potassium carbonate, sodium
hydrogencarbonate and potassium hydrogencarbonate, an alkaline earth
hydroxide, such as calcium hydroxide, magnesium hydroxide and barium
hydroxide, an alkaline earth oxide, such as calcium oxide, and an alkaline
earth carbonate, such as calcium carbonate.
The nucleating agent is not limited to the above compounds, and any known
nucleating agent may be employed. Moreover, two or more nucleating agents
may be used simultaneously. A suitable blending amount of inorganic
nucleating agent is 0.01 to 5 wt. %, preferably 0.05 to 3 wt. %.
Preferable nucleating agents are organic nucleating agent of
dibenzylidenesorbitol compounds, and the di-substituted
benzylidenesorbitol compositions described below are particularly
preferable for the polyolefin resins, preferably propylene-.alpha.-olefin
random copolymer resin, homopolyethylene resin having a density of not
less than 0.910 g/cm.sup.3 and ethylene-.alpha.-olefin copolymer resin
having a density of not less than 0.870 g/cm.sup.3, which belong to the
crystalline resin of the invention, in view of the improvement in physical
strength, rigidity and film molding speed, the decrease of molding
troubles, and the improvement in foreign odor and blending out which are
the defects of conventional organic nucleating agent.
The di-substituted benzylidenesorbitol composition contains solid powder of
the dibenzylidenesorbitol derivative represented by the following general
formula and the following higher fatty acid as the essential components,
and the surface of the solid powder of the dibenzylidenesorbitol
derivative is coated with the higher fatty acid.
##STR7##
In the formula, R and R' independently represent an atom or a group
selected from chlorine atom, methyl group and ethyl group, preferably
chlorine atom or methyl group.
CH.sub.3 (CH.sub.2).sub.n COOH
In the formula, n represents a number of 14 to 30, preferably 18 to 27,
particularly preferably 20 to 25. Preferable dibenzylidenesorbitol
derivatives of the above general formula are
1.3,2.4-di(p-methylbenzylidene)sorbitol, 1.3,2.
4-di(p-ethylbenzylidene)sorbitol,
1.3-p-methylbenzylidene-2.4-p-chlorobenzylidenesorbitol,
1.3-p-methylbenzylidene-2.4-p-ethylenzylidenesorbitol,
1.3-p-chlorobenzylidene-2.4-p-methylbenzylidensorbitol and the like.
Particularly preferable dibeyzylidenesorbitol derivatives are
1.3.2.4-di(p-methylbenzylidene)sorbitol,
1.3-p-methylbenzylidene-2.4-p-chlorobenzylidene sorbitol and
1.3-p-chlorobenzylidene-2.4-p-methylbenzyidenesorbitol.
Preferable higher fatty acids are behenic acid, stearic acid and palmitic
acid. Behenic acid is the most preferable, and stearic acid is in the
second place.
The particle size of the solid powder of the dibenzylidene sorbitol
derivative is not particularly limited, but a particle size distribution
of 30 to 100 mesh is preferred.
Preferable organic nucleating agent composition contains 95 to 50 parts by
weight, preferably 90 to 50 parts by weight, of the dibenzylidenesorbitol
and 5 to 50 parts by weight, preferably 10 to 50 parts by weight, of the
higher fatty acid so that the total of both components is 100 parts by
weight.
The di-substituted dibenzylidenesorbitol can be prepared by adding the
solid powder of the dibenzylidenesorbitol derivative to an aqueous
emulsion containing the higher fatty acid in the above ratio, stirring to
form a coating layer of the higher fatty acid on the surface of the solid
powder of the dibeyzylildenesorbitol derivative, filtering out the
dibeyzylidenesorbitol derivative powder coated with the higher fatty acid,
washing followed by drying. The above aqueous emulsion of the higher fatty
acid is prepared by dispersing an organic solvent solution of the higher
fatty acid in a concentration of 5 to 50 wt. %, preferably 10 to 50 wt. %
into water together with a small amount, such as 1 to 10 parts by weight,
preferably 2 to 5 parts by weight, of surfactant. The presence of the
higher fatty acid coating formed on the surface of the solid powder of the
dibenzylidene sorbitol derivative can be confirmed by coloring the coating
using a dye and then observing.
The pobenzylidenesin, to which the di-substituted benzylidenesorbitol
composition is blended as and additive in order to improve physical
strength and to decrease bleeding out and odor, includes homopolymers and
copolymers of aliphatic monoolefin having a number of carbon atoms of 2 to
6, such as homopolypropylene resin, low density homopolyethylene resin,
high density homopolyethylene resin, linear polyethylene
(ethylene-.alpha.-olefin copolymer) resin, ethylene-propylene copolymer
resin and the like, having a number average molecular weight of 10,000 to
1,000,000, preferably 15,000 to 500,000, more preferably 20,000 to
200,000, particularly preferably 30,000 to 150,000. The blending effects
of the organic nucleating agent are especially exercised on the polyolefin
resin having a high crystallinity, not less than 50%, preferably not less
than 70%, more preferably not less than 80%, particularly preferably not
less than 90%. A suitable molecular weight distribution (weight average
molecular weight/number average molecular weight) is 2 to 20, preferably 3
to 15, more preferably 3.5 to 12, particularly preferably 4 to 8.
A suitable blending amount of the di-substituted benzylidenesorbitol
composition is 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by
weight, per 100 parts by weight of the polyolefin resin.
The di-substituted benzylidenesorbitol composition can be blended into the
polyolefin resin by an arbitrary known blending means, and the blend
prepared in a high concentration can be used as a masterbatch resin.
In the di-substituted benzylidenesorbitol composition, it is important that
the surface of the solid particles of the dibenzylidenesorbitol derivative
is coated with the higher fatty acid, and the aforementioned effects
cannot be obtained by mere blending of the dibenzylidene sorbitol
derivative and the higher fatty acid.
Moreover, in order to obtain the aforementioned effects, a heat history of
not less than 180.degree. C., preferably not less than 190.degree. C.,
particularly preferably not less than 200.degree. C. is necessary. The
heat history is sufficient by once. For example, the polyolefin resin
composition is blended with 0.01 to 2 wt. % of the above di-substituted
benzylidenesorbitol composition, and pelletized with heating at a
temperature not less than 180.degree. C., preferably not less than
190.degree. C., particularly preferably not less than 200.degree. C. The
pellets are used for molding a light-shielding polyolefin resin film or
the like. Even when the molding resin temperature is less than 180.degree.
C., the aforementioned effects are obtained, by rendering the molding
resin temperature not less than 180.degree. C. (i.e. twice heat history of
not less than 180.degree. C.), the molded light-shielding polyolefin resin
film is very excellent in physical properties and rigidity, has a high
surface gloss and rare occurrence of wrinkling and streaks.
The di-substituted benzylidenesorbitol composition exhibits various
advantages compared with conventional organic nucleating agent, such as
not degrading various properties, such as physical strength, bleeding out
problem and rigidity, but occasionally improving the properties, being
excellent in odorless property, resistance to wrinkling and streaks, the
improvement in film moldability, film forming speed and the decrease of
molding trouble, by blending the polyolefin resin composition. That is,
light-shielding molded articles for photographic photosensitive materials
excellent in physical strength, rare bleeding out, odorless property, film
moldability and wear resistance can be provided by blending the polyolefin
resin composition of the invention with the di-substituted
benzylidenesorbitol composition.
Although the reason why the di-substituted benzylidenesorbitol composition
exhibits the above excellent effects is not clear, it can be considered
that benzaldehyde, which is a raw material of conventional
dibenzylidenesorbitol, and benzaldehyde derivatives such a p-substituted
benzaldehyde, which are a raw material of the dibenzylidene sorbitol
derivative of the invention, have odor, and a trace amount thereof
unavoidably remains in dibenzylidenesorbitol or its derivative after
purification to cause foreign odor of the light-shielding polyolefin
resin, and that a small amount of dibenzylidenesorbitol or its derivative
is decomposed during molding the light-shielding polyolefin resin film to
cause foreign odor. By satisfying the requirement of using the solid
particles of the dibenzylidenesorbitol derivative of the aforementioned
formula and coating them with the higher fatty acid of the aforementioned
formula, the di-substituted benzylidenesorbitol composition exhibits the
effect of sharply decreasing the foreign odor of the molded articles of
the invention and the effect of improving the aforementioned various
properties, such as rigidity and physical strength.
Various organic nucleating agent may be used as a nucleating agent or a
combination of two or more organic nucleating agent. The surface of
organic and/or inorganic nucleating agent may be coated with various
lubricant, such as fatty acid, fatty acid compound or silicone, coupling
agent, plasticizer, dispersing agent such as surfactant, wetting agent or
the like.
A suitable blending amount of nucleating agent is 0.005 to 5 wt. %,
preferably 0.01 to 3 wt. %, more preferably 0.03 to 2 wt. %, particularly
preferably 0.05 to 1 wt. % in total. When the blending amount is less than
0.005 wt. %, the blending effects is insufficient. When the blending
amount exceeds 5 wt. %, the effect of the excess amount of the nucleating
agent is minor. According to the kind of the nucleating agent, it
adversely affects photographic photosensitive materials, generates noxious
odor, adheres to mold, bleeds out, decreases dropping strength, or the
like.
As the method of blending the nucleating agent, there are the compound
method, the dry blending method, the masterbatch method, and the like, and
the masterbatch method is preferred. It is preferable to blend at the time
of producing coloring masterbatch, in view of cost and workability. Since
the nucleating agent is bulky and tends to fly away, to blend a small
amount of dispersing agent or wetting agent is preferred. Suitable
dispersing agents include various lubricants, various low molecular weight
polyolefin resins having a weight average molecular weight of 500 to
10,000, various waxes, various carboxylic acid anhydrides, various higher
fatty acids, etc., and lubricants such as various fatty acid metal salts,
various silicones and oleic amide are particularly preferred. As the
wetting agent, plasticizers such as DOP and DHP can be used.
It is also preferred to prevent the bleeding out by coating or blending a
fatty acid or a fatty acid compound, such as a higher fatty acid, a fatty
acid amide or a fatty acid metal salt onto or with the organic nucleating
agent. Furthermore, the blending effect of the nucleating agent is
improved by using in a form of pellets formed by blending with a
polyolefin resin having a heat history at not less than 180.degree. C.,
preferably not less than 190.degree. C., particularly preferably not less
than 200.degree. C. By blending these additives, physical strength is
improved, white powder generation caused by abrasion can be decreased by
increasing rigidity, and white powder generation caused by crystallization
or bleeding out of the organic nucleating agent can also be decreased.
Moreover, uncomfortable odor of the organic nucleating agent is prevented,
and antistatic ability and antiblocking ability are improved. In this
case, it is preferable to blend the aforementioned various antioxidant in
order to prevent the degradation, oxidative decomposition and coloring of
the above various dispersing agent and various thermoplastic resin.
By blending the nucleating agent, various effects are obtained. For
example, by blending 0.1 part by weight of p-t-butylbenzoate as the
nucleating agent with 100 parts by weight of propylene-ethylene copolymer
resin which is crystalline thermoplastic resin, haze can be decreased from
40% to 21%. When 0.2 part by weight is blended, haze is further decreased
to 12%. By blending 0.1 part by weight, tensile yield stress can be
improved from 380 kg/cm.sup.2 to 420 kg/cm.sup.2. Although a further
amount is blended, the tensile yield stress is improved scarcely. When 0.1
part by weight is blended, bending elastic modulus is improved by 500 to
600 kg/cm.sup.2. Although a further amount is blended, the bending elastic
modulus is improved scarcely.
The following additives may be added to the resin composition of the
invention.
(1) Plasticizer; phthalic acid esters, glycol ester, fatty acid esters,
phosphoric acid esters, etc.
(2) Stabilizer; lead compounds, cadmium compounds, zinc compounds, alkaline
earth metal compounds, organic tin compounds, etc.
(3) Flame retardant; phosphoric acid esters, phosphoric acid ester halides,
halides, inorganic materials, polyols containing phosphor, etc.
(4) Filler; alumina, kaolin, clay, zeolite, calcium carbonate, mica, talc,
titanium oxide, silica, etc.
(5) Reinforcing agent; glass lobing, metallic fiber, glass fiber, glass
milled fiber, carbon fiber, etc.
(6) Blowing agent; inorganic blowing agents (ammonium carbonate, sodium
hydrogen carbonate), organic blowing agents (nitroso compounds, azo
compounds) etc.
(7) Vulcanizing; vulcanization accelerator, acceleration assistant, etc.
(8) Deterioration preventing agent, ultraviolet absorber, metal
deactivator, peroxide decomposing agent, etc.
(9) Coupling agent; silane compounds, titanium compounds, chromium
compounds, aluminum compounds, etc.
(10) Various thermoplastic resins, polyolefin, elastomers, rubbers.
The following plasticizer may be blended into the molded article for
photographic photosensitive materials in order to improve uniform
dispersibility of the light-shielding material.
(1) Phthalic acid plasticizer
dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisodecyl
phthalate, butyl lauryl phthalate, ditridecyl phthalate, butyl benzyl
phthalate, butyl phthalyl butyl glycolate, etc.
(2) Phosphoric acid plasticizer
tricresyl phosphate, trioctyl phosphate, etc.
(3) Fatty acid plasticizer
tri-n-butyl citrate, dioctyl adipate, dioctyl azelate, dioctyl sebacate,
methyl acetyl ricinoleate, etc.
(4) Epoxy plasticizer
alkyl epoxy stearate, 4,5-epoxytetrahydrodiisodecyl phthalate, etc.
(5) Other plasticizer
chlorinated paraffin, polyester, sucrose octacetate, etc.
A suitable blending amount of the plasticizer is 0.01 to 10 wt. %,
preferably 0.05 to 7 wt. %, particularly preferably 0.1 to 5 wt. %. When
the blending amount is less than 0.01 wt. %, the blending effects of the
improvement in the uniform dispersibility of light-shielding material and
in the blocking adhesion is insufficient. When the blending amount exceeds
10 wt. %, screw slip occurs in an extruder resulting in the variation of
ejected resin amount.
As the deodorant, there are organic carboxylic acids, mixtures of organic
carboxylic acid and zinc compound, mixtures of organic carboxylic acid,
zinc compound and aluminum compound, etc.
The organic carboxylic acids include aliphatic polycarboxylic acids,
aromatic polycarboxylic acids, acidic polyester compounds which are
reaction product of the aliphatic or aromatic polycarboxylic acid and
polyol compound and has a carboxyl group at terminal(s), etc. As the
aliphatic polycarboxylic acids, there are various di-or tri-carboxylic
acids, such as oxalic acid, malonic acid, succinic acid, adipic acid,
fumaric acid, methylfumaric acid, maleic acid, methylmaleic acid, itaconic
acid, acetylenic acid, malic acid, methylmalic acid, citric acid,
isocitric acid, mesaconic acid, citraconic acid and their salts, and the
like, and citric acid and fumaric acid and their salts are particularly
preferred. As the aromatic polycarboxylic acids, there are phthalic acid,
terephthalic acid, isophthalic acid, trimellitic acid pyromellitic acid,
benzenehexatricarboxylic acid, naphthalene dicarboxylic acid, naphthalene
tricarboxylic acid, naphthalene tetracarboxylic acid, azobenzene
tetracarboxylic acid, and their anhydrides and the like, and benzene
tricarboxylic acid and trimellitic acid are particularly preferred. As the
acidic polyester compound having a carboxylic group at a terminal, there
are polyesters having a terminal carboxyl group produced by the reaction
of polycarboxylic acid such as phthalic acid with polyol such as ethylene
glycol or diethylene glycol, acidic cellulose derivatives modified with
polycarboxylic acid, and the like.
The zinc compound combined with the organic carboxylic acid includes zinc
oxide, inorganic zinc salts, such as zinc chloride, zinc sulfate, zinc
phosphate and zinc carbonate, and organic zinc salts, such as zinc citrate
and zinc fumarate. A suitable mixing ratio of organic carboxylic acid:zinc
compound is 1:0.1-3 by weight ratio.
The aluminum compound combined with the organic carboxylic acid and the
zinc compound includes aluminum sulfate and potassium alum, and a suitable
mixing ratio of organic carboxylic acid : zinc compound : aluminum
compound is 1:0.1:0.1 to 1:3:3 by weight ratio.
As the oxygen scavenger, there are sulfites hydrogen sulfites, dithionates,
hydroquinone, catechol, resorcin, pyrogallol, gallate, ascorbic acid,
ascorbate, isoaccorbic acid, isoascorbate, glucose, lignin,
dibutylhydroxytoluene, butylhydroxyanisole, ferrous salts, metal powders
such as iron powder, carbon dioxide-generating type oxygen scavengers,
carbon dioxide-absorbing type oxygen scavengers, cristobalite, zeolite,
hydrosulfite, glucose oxidase, sarcosine, alkali metal sulfides, alkali
carbonates, sodium thiosulfate, sodium alum, disodium hydrogen
phosphate.12 hydrates, hydrous sodium silicate, hydrous sodium borate,
ferrous silicate sulfates.7 hydrates, activated clay, mordenite, and the
like. The oxygen scavenger may be used as a single material or a
combination of them. Preferable oxygen scavengers are those containing
hydrosulfite as the principal component, those containing organic material
such as L-ascorbic acid as the principal component, those containing iron
powder as the principal component, mixture compositions of iron and at
least one material selected from the group consisting of ferrous silicate
sulfate.7 hydrate, sodium alum, disodium hydrogen phosphates.12 hydrates,
hydrous sodium silicate and hydrous sodium borate, hydrosulfite and
calcium hydroxide or sodium bicarbonate and activated carbon, iron powder,
accelerating salt and hydrous material, oxidizable metal powder and sodium
thiosulfate and solid reaction assistant, iron powder and sodium
thiosulfate and activated carbon, activated iron oxide, metal oxides,
palladium, sugars, enzymes, and the like.
As the moisture absorber, there are water-absorptive resins containing
carboxyl group, alkali metal salts of crosslinking polyacrylate, ethylene
copolymer resins containing carboxyl group, alkali metal salt of
acrylate-graft starch crosslinking agent, crosslinked polyvinyl
alcohol-alkali metal salt of acrylate copolymer, crosslinked polyvinyl
alcohol-maleic anhydride copolymer, modified celluloses, water-soluble
polymer crosslinking agent, self-crosslinking type alkali metal salt of
acrylate copolymer, polyacrylic acid and alkali salts thereof,
polyacrylamide and partial hydrolyzate thereof, polyvinyl pyrrolidone,
sulfonated polystyrene, polyacrylamide-2-methylpropane sulfonic acid
sodium salt, graft copolymer of starch-acrylonitrile and hydrolyzate
thereof, hydrolyzate of polyacrylonitrile, copolymer of acrylamide and
acylic acid, carboxymethyl cellulose, vinyl styrene sulfonic acid, Mannich
reaction product of polyacrylamide, polyacrylamine,
dimethylaminoethylmethacrylate homopolymer and copolymer thereof with
acrylamide, homopolymer of quaternary ammonium salt of
dimethylaminoethylmethacrylate produced by methyl chloride and copolymer
thereof with acrylamide, quaternary ammonium salt of
polydimethylallylamine, polymer of quaternary vinyl benzlamine,
acetylating agent of chitosan, condensation product of epichlorohydrin and
polyvalent amine or monoamine, resin prepared by adsorbing polyamide
polyamine epichlorohydrin thermosetting resin on the surface of high
water-absorptive resin beads followed by thermosetting, copolymer of
hydrophilic vinyl monomer (acrylamide derivative, etc.) and hydrophobic
vinyl monomer (methacrylate derivative, etc.), sodium salt of
isobutylene-maleic anhydride copolymer, sodium salt of starch and acrylic
acid and acrylic acid derivative graft copolymer, partially crosslinked
carboxymethyl cellulose-polybasic acid, partially crosslinked polyacrylic
acid, surface-coated high water-absorptive polymer, blends of high
water-absorptive polymer and inorganic material (attapulgite, kaolin,
talc, diatomaceous earth, etc.), mixture of high water-absorptive resin
having anionic dissociative group and high water-absorptive resin having
cationic dissociative group, starch-acrylic acid-sodium acrylate
copolymer, starch-sodium acrylate copolymer, etc. Preferable moisture
absorbers are produced from starch, cellulose or synthetic polymer having
a great water absorbability.
It is preferable to add inorganic material having ion-exchange ability in
order to adsorb gases which adversely affect photographic properties of
photographic photosensitive materials to render harmless, to improve
dispersibility by combining light-shielding material, to react with
unfavorable odor substances to render odorless. As the inorganic material
having ion-exchange ability, there are 1 various zeolite including natural
zeolite, such as analcime, erionite or mordenite, and synthetic zeolite in
a type of A, N-A, X, Y, hydroxy sodalite, B, R, T, hydroxy cancrinite or
the like, having a mean particle size of 0.1 to 7 .mu.m, preferably 0.1 to
5 .mu.m, particularly preferably 0.1 to 3.5 .mu.m, and a suitable content
in the resin composition being 0.1 to 10 wt. %, preferably 0.2 to 8 wt. %,
particularly preferably 0.3 to 6 wt. %, and exercising various effects,
such as the improvement in dispersibility, deodorization effect and
adsorption of harmful gases to photographic properties, by combining
light-shielding material, 2 diatomaceous earth, 3 activated clay, 4
synthetic aluminum silicate, 5 synthetic calcium silicate, 6 synthetic
magnesium silicate, 7 mica, 8 chelating material, etc. Examples of the
chelating material are carboxylic acid-type phthalocyanine metal complex,
such as metal phthalocyanine tetracarboxylic acid and metal phthalocyanine
octacarboxylic acid, iminodiacetic acid-type chelate resin,
aminocarboxylic acid-type chelate resin (ethylenediamine-tetraacetic acid
(EDTA), etc.), polyamino-type chelate resin, glucamine-type chelate resin,
carrier-type chelate resin, 4-dimethylamino-2.6-pyridine dicarboxylic acid
chelate resin, and the like. A suitable blending amount of the inorganic
material having ion-exchange ability is 0.01 to 10 wt. %, preferably 0.05
to 8 wt. %, more preferably 0.1 to 6 wt. %. When the blending amount is
less than 0.01 wt. %, the blending effect is insufficient. When the
blending amount exceeds 10 wt. %, the effect obtained by the excess amount
is small. Moreover, the decrease of physical strength and the degradation
of appearance occur.
The agent imparting fragrance are natural fragrant components, such as
ethereal oil of lilac flower, jasmine, abies oil, cinnamon oil, lavender
oil and lemon oil, and synthetic fragrant components, such as geraniol,
eugenol, n-octyl alcohol, carbitol, cis-jasmone, lemon terpene, menthone,
methylsalicylate, methylphenylcarbinol, triethyl citrate, benzyl
benzolate, citral, d-limonene, ethylcinnamate, alkylene glycol,
benzylsalicylate, linalool, varillin, coumarin, methyl naphthyl ketone and
rose phenone, which are used by encapsulating to form microcapsules or
entrapping by cyclodextrin, maltosyl cyclodextrin, zeolite, starch, talc
or the like.
One or more of the oxygen scavenger, deodorant, moisture absorber, the
agent imparting fragrance or inorganic material having ion-exchange
ability (including chelating material, and a suitable content is 0.01 to
20 wt. %, preferably 0.05 to 10 wt. %, more preferably 0.1 to 5 wt. %.
Taking into consideration the case of reclamation treatment as waste,
degradable plastic which is being developed or has already introduced in
the market can be used. For example, a biodegradable polymer of "BIOPOL"
(ICI), "Polycaprolactone" (UCC) or the like is utilized, or a polymer
indirectly collapsed by blending a biodegradable natural or synthetic
polymer as an additive, such as polyethylene blended with starch, can be
utilized. In order to improve industrial waster treatment, it is also
preferable to blend a recently commercialized synthetic biodegradable
plastic which can be decomposed up to carbon dioxide and water by the
action of microorganisms ("Bionol", Showa Polymer, which is a special
polyester resin synthesized from dicarboxylic acid and the like, a polymer
alloy of modified polyvinyl alcohol having biodegradability and maize
starch) in an amount of not less than 10 wt. % of the resin composition
for the molded article of the invention. In the case of a multilayer
molded article, it is preferable so that the layer(s) which do not contact
directly photographic photosensitive materials contain not less than 50
wt. % of the above biodegradable plastic in view of the improvement in
industrial waste treatment.
Moreover, it is also possible to utilize a photodegradable polymer, such as
ELO copolymer wherein carbonyl groups are introduced into the main chain
as a photosensitization group at the time of polymerization of ethylene,
i.e. copolymerization of ethylene and carbon monoxide, polymers to which
photodegradability is imparted by adding transition metal salt, oxidation
accelerator, photosensitizer or the like to base polymer. It is also
possible to combine degradable polymers, such as biodegradable polymer,
photodegradable polymer and water-soluble polymer (Japanese Patent KOKAI
No. 3-129341).
Representative examples of the molded article for photographic
photosensitive materials of the invention formed by molding the above
resin composition are as follows:
Films: Single layer films (FIG. 1, Japanese Patent KOKOKU No. 2-2700,
etc.), coextruded multilayer films (FIGS. 2, 3), laminated films using a
single layer film or a coextruded multilayer film (FIGS. 4-7, Japanese
Patent KOKOKU Nos. 63-26697, 2-2701, 2-13774, 2-19225, etc.), packaging
materials using the above flexible sheet of the single layer film,
coextruded multilayer film or laminated film, such as packaging bags
(unipack bag, single sheet flat bag, double sheet flat bag, single sheet
gusset bag, double sheet gusset bag, etc.), shrink packaging, bulk
packaging (Japanese Patent KOKAI No. 3-53243, Japanese Utility Model KOKAI
No. 3-71346, etc.), assembly packaging, and the like and package for light
room loading of a band form photosensitive material (Japanese Utility
Model KOKAI Nos. 55-113543, 60-13386, 60-167796, 2-72347, 3-47547,
3-54937, 3-86358, 3-96648, etc.)
Vacuum-molded articles:
Injection-molded articles: spool for photographic film, film unit with
lens, container for photographic film cartridge, light-shielding
container, cartridge for photographic film, light-shielding magazine for
light room loading, core, photographic film cartridge, pack for instant
film, etc.
Cartridge for disc film: Japanese Utility Model KOKAI No. 60-21743, etc.
Film unit with lens: Japanese Patent KOKAI No. 63-226643 (FIG. 12)
Spool for photographic film: Japanese patent KOKAI Nos. 1-251030,
57-196218, 59-15049, 58-203436, 58-82237, 58-82236, 62-240957, Japanese
Utility Model KOKAI Nos. 63-73742, 54-120931, 58-178139-178145, 63-73742,
Japanese Utility Model KOKOKU Nos. 55-31541, 44-16777, U.S. Pat No.
1,930,144, GB 2199805A (FIG. 10)
Cartridge for photographic film: Japanese Patent KOKAI Nos. 54-111822,
50-33831, 56-87039, 1-312538, 57-190948, Japanese Patent KOKOKU Nos.
45-6991, 55-21089, Japanese Utility Model KOKAI No. 55-97738, U.S. Pat No.
4,846,418, U.S. Pat No. 4,848,693, U.S. Pat No. 4,887,776, etc. (FIG. 11)
Container for photographic film cartridge: Japanese Patent KOKAI Nos.
61-250639, 61-73947, 63-121047, 62-291639, Japanese Utility Model KOKAI
Nos. 60-163451, 1-88940, 1-113235, 1-152337, Japanese Utility Model KOKOKU
Nos. 2-33236, 3-48581, Japanese Patent KOKOKU No. 2-38939, U.S. Pat No.
4,801,011, U.S. Pat No. 4,979,351, EP 0237062A2, EP 0280065A1, EP
0298375A2, etc. (FIGS. 8, 9)
Core, Reel: Japanese Utility Model KOKAI No. 60-107848, U.S. Pat No.
4,809,923, GB 2,033,873 B, etc.
Magazine for sheet films: Japanese Utility Model KOKAI No. 56-5141, etc.
Photographic film cartridge: Japanese Patent KOKAI No. 1-312537, Japanese
Utility Model KOKAI Nos. 2-24846, 2-29041, 60-120448, Japanese Utility
Model KOKOKU No. 56-16610, etc. (FIG. 14)
Photographic film case: Japanese Utility Model KOKAI No. 54-100617,
64-32343, 1-94258, 2-56139, Japanese Patent KOKOKU No. 2-54934, U.S. Pat.
No. 4,779,756, EP 0242905A1, etc. (FIG. 13)
The method of forming the molded article for photographic photosensitive
materials may be selected from inflation film molding, injection molding
vacuum molding, sheet forming, T die flat film molding, pressure forming,
rotational molding, intermold vacuum injection molding and the like,
according to the form of each article to be molded.
The molded article of the invention may be provided with letters and marks
which are required on the functional view point or with print in order to
improve the value as commercial goods. The ink used for printing them can
be selected from harmless inks to photosensitive materials among
conventional inks for offset printing, inks for gravure printing or UV
inks.
Representative synthetic resins used or the inks are vinyl chloride
copolymer resins, vinyl-amino resin, alkyd-vinyl resin, oil-free alkyd
resin, vinyl chloride-vinyl acetate copolymer resins, nitrocellulose,
polyester, polyamide-urethane, polyacrylic resin, rosin-modified maleic
acid resin, ethylene-vinyl acetate resin, vinyl ether resin, urethane
vinyl acetate resin, vinylchloride-vinylacetate copolymer urethane resin,
modified alkyd resin, modified phenol resin, high molecular weight
polyester-amino resin, low molecular weight polyester-amino resin,
alkali-soluble resins (rosin-modified maleic acid resin, styrene-maleic
acid resin, styrene-acrylic acid resin, acrylate ester-acrylic acid resin,
methacrylate ester-acrylic acid resin), hydrosol type resins
(styrene-maleic acid resin, styrene-acrylic acid resin,
.alpha.-methylstyrene-acrylic acid resin, acrylate ester-acrylic acid
resin, methacrylate ester-acrylic acid resin), emulsion type resins
(styrene resin, styrene-acrylate ester resin, acrylate ester copolymer
resins, methacylate ester copolymer resins), and the like. As the resins
used for UV ink, polymers having acrylic unsaturated groups are, in
general, used, and representative examples are polyester/acrylate ester,
polyester/urethane resin/acrylate ester, epoxy resin/acrylate ester,
pentaerythritol triacrylate, trimethylol propane triacrylate, hexanediol
diacrylate, neophentylglycol diacrylate, triethylene glycol diacrylate,
hydroxyethyl methacrylate, etc.
Coloring pigments generally known are used for the above inks. The coloring
pigments include various pigments disclosed in Japanese Patent KOKAI No.
63-44653, etc., azo pigments, (Azo Lake, Carmine 6B, Red 2B, insoluble azo
pigments, Monoazo Yellow (PY-1,-3), Disazo Yellow (PY-12,-13,-14,-17,-83),
Pyrazolo Orange (PO-B-34), Vulcan Orange (PO-16), condensed azo pigments,
Chromophthal Yellow (PY-93,-95), Chromophthal Red (PR-144,-166)),
polycyclic pigments (phthalocyanine pigments, Copper Phthalocyanine Blue
(PB-15,-15.1,-15.3), Copper Phthalocyanine Green (PG-7)), dioxane pigments
(Dioxane Violet (PV-23)), isoindolinone pigments (Isoindolinone Yellow
(PY-109,-110)), durene pigments, perillene, perinone, flavanthrone,
thoindigo, lake pigments (Malachite Green, Rhodamine B, Rhodamine G,
Victoria Blue B), inorganic pigments, such as oxides (titanium dioxide,
red ion oxide), sulfates (precipitated barium sulfate), carbonates
(precipitated calcium carbonate), silicates (hydrous silicates, anhydrous
silicates), metal powders (aluminum powder, bronze powder, zinc powder),
carbon black, lead yellow, Ultramarine blue, Berlin blue, and the like.
These pigments may be added to the aforementioned resin layers or the like
as a light-shielding material. In addition, oil-soluble dyes, disperse
dyes, and the like are also usable. Other raw materials composing the ink
which are optional are various solvent, dispersing agent, wetting agent,
antifoamer, leveling agent, thickener, stabilizer, crosslinking agent, wax
and the like.
It is also preferable to use the above synthetic resins and coloring
pigments as paint for coating the molded article for the purpose of the
improvement in the commercial value, wear resistance, light-shielding
ability, photographic properties or the like.
The molded article for photographic photosensitive materials of the
invention is applicable to the following photosensitive materials.
Silver halide photographic photosensitive materials: films for printing,
color and monochrome photographic printing papers, color and monochrome
films, master papers for printing, DTR (diffusion transfer process)
photosensitive materials, films and papers for computerized type-setting
system, color and monochrome positive films, color reversal films,
microfilms, films for movie, self-developing type photographic
photosensitive materials, direct positive films and papers, etc.
Heat developing photosensitive materials: heat developing color
photosensitive materials, heat developing monochromatic photosensitive
materials, e.g. disclosed in Japanese Patent KOKOKU Nos. 43-4921, 43-4924,
"Shashinkogaku-no-Kiso (Fundamentals of Photographic Engineering), Vol.
Silver Salt Photograph", pp 553-555, Corona, 1979, "Research Disclosure",
pp 9-15 (RD-17029), June, 1978, transfer-type heat developing color
photosensitive materials disclosed in Japanese Patent KOKAI Nos. 59-12431,
60-2950, 61-52343, U.S. Pat No. 4,584,267, etc.
Photosensitive heatsensitive recording materials: recording materials using
photothermography (photosensitive heatsensitive image forming method)
disclosed in Japanese Patent KOKAI No. 3-72358.
Diazonium photographic photosensitive materials: 4-morpholinobenzene
diazonium microfilms, microfilms, copying films, form plates for printing,
etc.
Azide, diazide photographic photosensitive materials: photosensitive
materials containing parazidobenzoate, 4,4'-diazidostilbene, etc., such as
copying films and form plates for printing etc.
Quinone diazide photographic photosensitive materials: photosensitive
materials containing ortho-quinone diazide compounds or
ortho-naphthoquinone diazide compounds, such as
benzoquinone-(1,2)-diazido-(2)-4-sulfonic acid phenyl ether, such as form
plates for printing, copying films and contact printing film, etc.
Photo polymers: photosensitive materials, form plates for printing, contact
printing films, containing vinyl compound monomer, etc.
Polyvinyl cinnamate esters: printing films, photoresists for IC, etc.
Moreover, the packaging material of the invention is also applicable to
various photosensitive materials degraded or denatured by light, oxygen,
sulfur dioxide gas or the like, such as foods including peanuts with
butter, margarine, snacks, relishes, cakes, teas and lavers, medicines
including powder and granular medicines placed in a bag for stomach and
bowels and for cold, dyes, pigments, photographic developing agent,
photographic fixing agent, toners and the like.
In the molded article for photographic photosensitive materials of the
invention, the antioxidant and the acrylic acid copolymer resin retard the
bleeding out of the lubricant, the antistatic agent and the like. The
oil-absorptive material absorbs the lubricant, the antistatic agent and
the like to prevent the bleeding out of them. The antioxidant also
inhibits the generation of materials which adversely affect photographic
properties of photographic photosensitive materials by the thermal
decomposition of resins or additives. As a result of decreasing the
bleeding out with time of the lubricant and the antistatic agent,
lubricating ability and antistatic ability can be kept for a long period,
and the generation of white powder caused by the bleeding out can be
decreased. Fogging and sensitivity deviation of the photographic
photosensitive materials can also be decreased.
By coating the surface of the light-shielding material with the
aforementioned surface-coating material, the dispersibility of the
light-shielding material in the resin composition is improved. As a
result, various advantages are obtained, such as the prevention of adverse
affects on photographic properties of the photographic photosensitive
materials, a sharp increase of light-shielding ability, decrease of lump
generation, decrease of coloring roubles, improvement in appearance, etc.
Some molded articles for photographic photosensitive materials embodying
the invention are illustrated in FIGS. 1 through 18.
FIGS. 1 through 9 illustrate films.
The film for photographic photosensitive materials of FIG. 1 is a single
layer film consisting of a light-shielding thermoplastic resin film layer
1a.
The film for photographic photosensitive materials of FIG. 2 is a
coextruded double layer film IIa consisting of a light-shielding
thermoplastic resin film layer 1a and a thermoplastic resin film layer 2.
The film for photographic photosensitive materials of FIG. 3 is the same as
the film of FIG. 2, except that the thermoplastic resin film layer 2a also
contains a light-shielding material.
The film for photographic photosensitive materials of FIG. 4 is a
coextruded triple layer film IIIa consisting of a light-shielding
thermoplastic resin film layer 1a, an intermediate layer 3 and a
thermoplastic resin film layer 2.
The film for photographic photosensitive materials of FIG. 5 is a laminated
film IVa consisting of two coextruded double layer films IIa of FIG. 2
joined by blocking B between the thermoplastic resin film layers 2,2.
The film for photographic photosensitive materials of FIG. 6 is a laminated
film IVa consisting of two coextruded double layer films IIa of FIG. 3
joined by blocking B between the thermoplastic resin film layers 2a, 2a.
The film for photographic photosensitive materials of FIG. 7 is a laminated
film consisting of the single layer film of FIG. 1 consisting of a
light-shielding thermoplastic resin film layer 1a and a flexible sheet
layer 5 laminated through an adhesive layer 4.
The film for photographic photosensitive materials of FIG. 8 is a laminated
film consisting of the single layer film of FIG. 1 consisting of a
light-shielding thermoplastic resin film layer 1a, a metallized biaxially
stretched film layer 9 consisting of a biaxially stretched film layer 6,
on which a metal vacuum deposition layer 8 deposited through an anchor
coat layer 7, laminated thereon through an adhesive layer 4 and a flexible
sheet layer 5 laminated further thereon through an adhesive layer 4.
The film for photographic photosensitive materials of FIG. 9 is a laminated
film consisting of the single layer film of FIG. 1 consisting of a
light-shielding thermoplastic resin film layer 1a, a metal foil 10
laminated thereon through an adhesive layer 4 and a flexible sheet layer 5
laminated further thereon through an adhesive layer 4.
FIG. 10 through 12 illustrate containers for a photographic film cartridge.
The containers 14 for a photographic film cartridge of FIGS. 10 and 11 are
a cap separated from body type, and consists of a container body 15 and a
cap 16. Both of the container body 15 and the cap 16 are the molded
article embodying the invention. Both containers are the same, except that
the container body 15 of FIG. 11 is tapered having a greater inside
diameter (A+.alpha.) of the upper opening portion than the inside diameter
(A) of the bottom portion so that stacking is possible.
The container 14 for a photographic film cartridge of FIG. 12 is a cap-body
integrated type consisting of a container body 15 portion and a cap 16
portion, and is formed of the thermoplastic resin composition of the
invention.
FIG. 13 illustrates a spool 20 for a photographic film, the whole body of
the spool is formed of the light-shielding thermoplastic resin of the
invention.
FIG. 14 illustrates an exploded state of a photographic film cartridge 17
consisting of an upper casing 18 and a lower casing 19, which constitute
the cartridge body, and a spool 20 on which the photographic film 35 to be
loaded is wound. All of the upper casing 18, the lower casing 19 and the
spool 20 are formed of the light-shielding thermoplastic resin composition
of the invention.
FIG. 15 illustrates an exploded state of a photographic film unit 21 with
lenz, consisting of a lower casing 22 in which a light-shielding
photographic film cartridge 17 containing a photographic film wound around
a spool 20 is set in a state shielded from light and an upper casing 23
which seals the lower casing 22 so as to form a light-shielding condition.
All of the spool 20, the lower casing 22 and the upper casing 23 are
formed of the light-shielding thermoplastic resin composition of the
invention.
FIG. 16 illustrates a cap-body integrated type case 24 for a photographic
film consisting of a container body 15 portion and a cap 16 portion, and
is formed of the light-shielding thermoplastic resin composition of the
invention.
FIG. 17 illustrates an exploded state of a photographic film cartridge 25
consisting of a lower casing 26, an upper casing 27 and a spool 28 loaded
therein, and all of the lower casing 26, the upper casing 27 and the spool
28 are formed of the light-shielding thermoplastic resin composition of
the invention.
FIG. 18 illustrates a packaging process of a package of a roll of
photographic photosensitive material. In the figure, a thermoplastic resin
film guide member 30 is joined to the leading end of the roll of,
photographic photosensitive material 29 wound around a core 33. A
light-shielding thermoplastic resin film cover member 31 is joined near
the base end of the guide member 30. After the guide member 30 is wound
entirely, both flap portions of the cover member 31 are gusseted toward
the opening end of the core 33, and the gusseted end is fixed by inserting
a bush 34 into the opening end of the core 33,32 indicates joining
portions.
EXAMPLES
Example 1
A single layer film consisting of a light-shielding thermoplastic resin
film layer 1a corresponding to FIG. 1 was formed by the inflation process.
The molding resin composition was a polyolefin resin composition consisting
of;
100 parts by weight of crystalline resin composition consisting of 70 parts
by weight of ethylene-4-methylpentene-1 copolymer resin having a MFR
(ASTSM D-1238, indicated by the number of grams of ejected polyethylene
resin from an orifice 2.095 mm in diameter, 8.0 mm in length for 10
minutes at 190.degree. C..+-.0.5.degree. C. at a load of 2.16 kg) of 2.0
g/10 minutes, a density (ASTM D-1505) of 0.920 g/cm.sup.3 and a
crystallinity of 45%, 10 parts by weight of homopolyethylene resin having
a MFR of 14 g/10 minutes, a density of 0.950 g/cm.sup.3 and a
crystallinity of 83%, 19.5 parts by weight of homopolyethylene resin
having a MFR of 2.0 g/10 minutes, a density of 0.925 g/cm.sup.3 and a
crystallinity of 67% as the crystalline resins, 0.05 part by weight of
erucic acid amide as the lubricant and 0.2 part by weight of nonionic
antistatic agent of glycerine monostearate as the antistatic agent,
0.10 part by weight of hindered phenolic antioxidant of tetrakis
[methylene-3(3e5-di-tert-butyl-4-hydroxyphenyl) propionate] methane and
0.05 part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate as the
antioxidant,
30 parts by weight of ethylene-acrylic acid copolymer resin having a MFR of
5.5 g/10 minutes, a density of 0.932 g/cm.sup.3 and an acrylic acid
content of 6.5 wt. % as the ethylene-acrylic acid copolymer resin, and
3.3 parts by weight of furnace carbon black having a pH of 8.0, a volatile
component content of 0.8 wt. %, an oil absorption value of 76 ml/100 g and
a mean particle size of 21 m.mu. as the light-shielding material.
Using the above polyolefin resin composition, the single layer film 70
.mu.m in thickness of a light-shielding polyolefin resin inflation film
was formed by an inflation film molding machine having a ring die 50
cm.phi. in diameter with a lip clearance of 1.1 mm, at a resin temperature
of 190.degree. C. at a blow-up ratio of 1:1.2.
The light-shielding inflation film was excellent in antistatic ability and
slipping character, and the bleeding out with time of the antistatic agent
and the lubricant was small. Greasiness and blocking did not occur, and
heat sealing properties were excellent.
Comparative Example 1
A single layer film 70 .mu.m in thickness was formed by the inflation
process using the same resin composition as Example 1, except that 30
parts by weight of homopolyethylene resin having a MFR of 5.0 g/10
minutes, a density of 0.919 g/cm.sup.3 and a crystallinity of 65% was
blended instead of 30 parts by weight of the ethylene-acrylic copolymer
resin, and that 2 kinds of the antioxidant were not added. The molding
machine and the molding conditions were also the same as Example 1.
In the light-shielding inflation film, the bleeding out with time of the
antistatic agent and the lubricant was great, and greasiness and blocking
occurred. Heat sealing properties were inferior. Moreover, photographic
properties were adversely affected, and lumps of microgrits were
frequently generated.
Conventional Example 1
A single layer film 70 .mu.m in thickness was formed by the inflation
process using a resin composition consisting of 99.75 parts by weight of
homopolyethylene resin having a MFR of 2.0 g/10 minutes, a density of
0.925 g/cm.sup.3 and a crystallinity of 67%, 0.05 part by weight of erucic
acid amide as the lubricant, 0.2 part by weight of glycerine monostearate.
The molding machine and the molding conditions were the same as Example 1.
In the inflation film, the bleeding out with time of the antistatic agent
and the lubricant was great, and greasiness and blocking occurred. Heat
sealing properties were inferior.
Example 2
A laminated film corresponding to FIG. 8 was molded.
Using the light-shielding polyolefin resin inflation film 1a 70 .mu.m in
thickness of Example 1, an aluminum vacuum deposited biaxially stretched
film layer 9 consisting of a biaxially stretched nylon resin film 6 of a
thickness of 15 .mu.m on which an aluminum vacuum deposition layer 8 of a
thickness of 400 .ANG. was formed through an anchor coat layer 7 of a
thickness of 2 .mu.m was laminated thereon through an extrusion laminating
low density homopolyethylene resin adhesive layer 4 of a thickness of 13
.mu.m formed at a resin temperature of 315.degree. C. As the flexible
sheet layer 5 an unbleached kraft paper having an areal weight of 70
g/m.sup.2 not effecting adversely photographic photosensitive materials
was laminated further thereon through an extrusion laminating low density
homopolyethylene resin adhesive layer 4 of a thickness of 13 .mu.m formed
at a resin temperature of 305.degree. C. to complete the laminated film.
Two sheets of the laminated films were joined between the light-shielding
polyolefin resin inflation film layers 1a, 1a by heat sealing to form a
light-shielding sealing bag, and a roll of color printing paper 8.9 cm in
width 180 m in length wound around a paper core 7.6 cm in outer diameter 8
mm in wall thickness facing the photographic emulsion layer on the outside
was packaged in a gussets bag form having a center seal and gussets to
complete a sealed package.
The package was excellent in light-shielding ability, antistatic ability
and physical strength. After storing for 1 year, sealing light-shielding
ability was still excellent, and decrease of heat seal strength was small.
Antistatic ability was excellent, and bleeding out onto the
light-shielding inflation film layer surface was moderate. No blocking to
the photographic emulsion layer, development inhibition by the transfer to
the photographic emulsion layer nor the adhesion of white powder occurred.
The outermost portion of the roll of color printing paper which was out of
quality assurance as a guide portion could be used for printing
photographs.
Example 3
A laminated film corresponding to FIG. 9 was molded.
The same laminated film as Example 2 was prepared, except that an aluminum
foil 7 .mu.m in thickness as the metal foil 10 was substituted for the
aluminum vacuum deposited biaxially stretched film layer 9, and a package
of a roll of color printing paper was prepared similar to Example 2.
The package also exercised unexpected results similar to Example 2 after
storing for 1 year.
Example 4
The same laminated film as Example 2 was molded, except that a biaxially
stretched polyester resin film 12 .mu.m in thickness was used instead of
the unbleached kraft paper as the flexible sheet layer 5 and the
light-shielding polyolefin resin inflation film 1a of Example 1 was used
as the innermost layer, and a package of a roll of color printing paper
was prepared similar to Example 2.
The package also exercised unexpected results similar to Example 2 after
storing for 1 year. Since a dust-free biaxially stretched polyester resin
film was used as the outermost layer, the package was further preferable
because of no generation of dust.
Comparative Example 2
The same laminated film as Example 4 was molded, except that the
light-shielding polyolefin resin inflation film 70 .mu.m in thickness of
Comparative Example 1 was used instead of the light-shielding polyolefin
resin inflation film 1a 70 .mu.m in thickness of Example 1 which was used
as the innermost layer in Example 2, and a package of a roll of color
printing paper was prepared similar to Example 2.
The package had similar properties to Example 2 initially, except of
frequent lump generation in the innermost layer, but, after 1 year,
bleeding out of erucic amide and glycerine monostearate onto the surface
was much, and transferred to the photographic emulsion layer of the roll
of color printing paper. Static marks were formed at the time of taking
out of the bag by the blocking to the photographic emulsion layer, and
uneven development based on the development inhibition occurred caused by
the transfer of erucic amide and glycerine monostearate. As a result, the
outermost round portion could not be used for printing photographs.
Conventional Example 2
The same laminated film as Example 2 was molded, except that the
light-shielding low density homopolyethylene resin inflation film 70 .mu.m
in thickness of Conventional Example 1 was used instead of the
light-shielding polyolefin resin inflation film la 70 .mu.m in thickness
of Example 1 which was the innermost layer in Example 2, and a package of
a roll of color printing paper was prepared similar to Example 2.
The package was remarkably inferior to Example 2 in sealing light-shielding
ability, heat seal strength, hot tack properties and the like from the
first. After 1 year, bleeding out of erucic amide and glycerine
monostearate onto the surface of the innermost layer was much. Heat seal
strength was decreased to about a half, and the heat-sealed portion was
occasionally separated by the weight of the roll alone. This is a great
problem for the light-shielding bag for photographic photosensitive
materials which require complete light-shielding. Moreover, bleeding out
of erucic amide and glycerine monostearate onto the surface was much, and
transferred to the photographic emulsion layer of the roll of color
printing paper. Static marks were formed at the time of taking out of the
bag by the blocking to the photographic emulsion layer, and uneven
development based on the development inhibition occurred caused by the
transfer of erucic acid amide and glycerine monostearate. As a result, the
outermost round portion could not be used for printing photographs.
Example 5
A container body corresponding to FIG. 10 was molded.
The molding resin composition was a polypropylene resin composition
consisting of;
100 parts by weight of polypropylene resin composition consisting of 99.85
parts by weight of propylene-ethylene random copolymer resin having a MFR
of 35 g/10 minutes, a density of 0.900 g/cm.sup.3 and a crystallinity of
93% as she crystalline resin, 0.05 part by weight of oleic acid amide as
the lubricant and 0.1 part by weight of polyoxyethylene sorbitan stearate
as the antistatic agent,
0.10 part by weight of hindered phenolic antioxidant of
tetrakis[methylene-3(3.5-di-tert-butyl-4-hydroxyphenyl) propionate]
methane and 0.10 part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate as the
antioxidant,
20 parts by weight of ethylene-acrylic acid copolymer resin having a MFR of
13 g/10 minutes, a density of 0.940 g/cm.sup.3 and an acrylic acid content
of 8 wt. % as the ethylene-acrylic acid copolymer resin, and
0.15 part by weight of 1.3,2.4-di-(methylbenzylidene) sorbitol of which the
surface had been treated with magnesium stearate as the organic nucleating
agent.
Using the above polypropylene resin composition, the container body for a
photographic film cartridge was formed by injection molding using an
injection molding machine using a mold having a number of cavities of 24
at a mold clamping pressure of 150 t at a resin temperature of 220.degree.
C. at a molding cycle of 8 seconds.
In the molded container bodies, coloring trouble and adverse affects on
photographic properties of photographic photosensitive materials did not
occur. Troubles caused by the bleeding out of lubricant, antistatic agent
or antioxidant did not occur, and fatal molding troubles, such as short
shot, was rare. Moreover, deformation also did not occur, and continuous
unmanned injection molding became possible for a long period.
The molded product of the container body for a photographic film cartridge
was excellent in shortening of molding cycle, in high speed pneumatic
conveying due to good slipping between the container bodies, resistance to
abrasion, antistatic properties, little adhesion of dust, and insertion of
a photographic film cartridge into the container body. Moreover,
appearance was very excellent, and dropping strength from 5 m height to
concrete floor was very great, and particularly, dropping impact strength
at a low temperature condition of not more than 0.degree. C. was greater
than twice that of the container body for a photographic film cartridge of
Comparative Example 3 not containing ethyene-acrylic acid copolymer resin.
After storing at 18.degree. C. for 1 year, bleeding out of the lubricant
of oleic amide and the antistatic agent of polyoxyethylene sorbitan
monostearate onto the surface of the container body was small, and
greasiness, dust adhesion and white powder generation were rare.
Appearance was excellent, and impact strength, slipping character and
antistatic properties were also excellent. Unexpectedly, it was found that
mold shrinkage caused by the gradual proceeding of crystallization of
polypropylene resin is decreased by blending ethylene-acrylic acid
copolymer resin.
Example 6
A container body corresponding to FIG. 10 was molded.
Using a light-shielding propylene-ethylene random copolymer resin
composition composed of the polypropylene resin composition of Example 5
blended with 5 parts by weight of titanium dioxide inorganic pigment of
which the surface was coated with zinc stearate as the light-shielding
material, the container body was molded using the same injection molding
machine and the same mold as Example 5 at a resin temperature of
220.degree. C. at a molding cycle of 7 seconds.
In molding the container body for a photographic film cartridge, fatal
molding troubles did not occur, and continuous unmanned injection molding
was possible for a long period. Appearance was also excellent. In the
molded product of the container body for a photographic film cartridge,
deformation, such as buckling or bottom sink mark did not occur, even
though the molding cycle was shortened by 1 second form Example 5. The
occurrence of coloring trouble was rare. Dropping strength was very
greater than Example 5, and the generation of cracking was 0% at ordinary
temperature (20.degree. C.). Dropping strength under low temperature
conditions at not more than 0.degree. C. was greater than Comparative
Example 3, and the generation of cracking was decreased to less than one
half. Nevertheless the container body was white opaque, even though the
container body was left under the sunlight for 3 hours, thermal
deformation did not occur. The container body was excellent in
heat-shielding, and temperature rise of the inside of container was not
great compared with Example 5. As a result, thermal deformation of the
spool contained in the cartridge did not occur, and degradation of
photographic properties of the photographic film scarcely occurred. Since
the color was white, transfer printability was excellent, and transferred
print was beautiful and had a high commercial value. Moreover, the
applicability to a curved surface high speed printer was also excellent.
After storing at 18.degree. C. for 1 year, bleeding out of the lubricant
of oleic amide and the antistatic agent of polyoxyethylene sorbitan
monostearate onto the surface of the container body was small, and
greasiness, dust adhesion and white powder generation were less than
Example 5 because of containing an oil absorption material titanium
dioxide. Moreover, white powder could not be seen by the synergistic
effect of white appearance.
Example 7
A container corresponding to FIG. 12 was molded which was a cap-body
integrated type square container for a photographic film cartridge wherein
the cap was integrated to the container body through a hinge.
Using the same propylene-ethyene random copolymer resin composition as
Example 6, the container was molded by injection molding using an
experimental mold having one cavity.
The properties of the molded container were excellent similar to Example 6.
Moreover, since the form was square, the container had stacking ability
and atore displaying ability. Moreover, decorated paper casket could be
omitted, and corporation identity (CI) mark and various prints were clear
because of a white opaque container. As described in Example 6, even
though the container was displayed at a store, the white opaque body
reflected the sunlight, and deformation of the container did not occur.
Temperature rise of the inside of the container was small. As a result,
thermal deformation of the spool contained in the cartridge was rare, and
degradation of photographic properties of the photographic film scarcely
occurred. Antistatic ability was excellent, and bleeding out of the
lubricant, the antioxidant and the nucleating agent onto the surface of
the container was small because of containing an oil absorption material
of titanium dioxide. Adhesion of dust was small. Industrial waste could be
decreased, and recycling use was many.
Comparative Example 3
A container body corresponding to FIG. 10 was molded.
Using the same propylene-ethylene random copolymer resin composition as
Example 5, except that 0.2 part by weight of two kinds of the hindered
phenolic antioxidant and 20 parts by weight of the ethylene-acrylic acid
copolymer resin were omitted, the container body was molded using the same
molding machine and the same mold as Example 5 at a molding cycle of 8
seconds.
The container body had excellent properties, dimensional accuracy and
transparency almost similar to Example 5, except that dropping strength
under low temperature conditions at not more than 0.degree. C. was
inferior, immediately after molding. However, after storing in a cold
storage room at 18.degree. C. for 1 year, crystallization proceeded, and
dropping strength at ordinary temperature was inferior to Example 5. The
lubricant of oleic acid amide and the antistatic agent of polyoxyethylene
sorbitan stearate were bled out of the surface, and white powder slightly
adhered onto the photographic film. Since hindered phenolic antioxidant
was not added, the resin was decomposed to produce aldehydes and the like
at retanded portions during continuous molding for a long period, and they
adversely affected photographic photosensitive materials, such as fogging
or sensitivity deviation. Resin yellowing occurred resulting in the
occurrence of coloring troubles, and lumps were generated to induce gate
clogging and short shot problem. Thus, unmanned continuous molding was
difficult.
Example 8
A container body corresponding to FIG. 10 was molded.
The molding resin composition was a homopolyethylene resin composition
consisting of;
98.8 wt. % of very high density homopolyethylene resin having a MFR (ASTM
D-1238) of 9 g/10 minutes, a density (ASTM D-1505) of 0.973 g/cm.sup.3, a
crystallinity (X-ray diffraction method) of 97%, a haze (ASTM D-1003) of
72%, a bending elastic modulus (ASTM D-790) of 15,600 kg/cm.sup.2, a Shore
hardness (ASTM D-2240) of 74D, a notched Izod impact strength (ASTM D-256)
at 23.degree. C. of 4.1 kg.multidot.cm/cm, a Vicat softening point (ASTM
D-1525) of 131.degree. C., a melting point (ASTM D-2117) of 140.degree. C.
and an elongation at rupture (ASTM D-638) of 358%, 0.1 wt. % of
1.1-diphenyl-2-picrylhydrazyl as the radical scavenger,
0.1 wt. % of a hindered phenolic antioxidant of pentaerythrityl-tetrakis
[3-(3.5-di-t-butyl-4-hydroxyphenyl) propionate] methane having a melting
point of not less than 100.degree. C., and 0.05 wt. % of a
phosphorus-containing antioxidant of an organic cyclic phosphorus compound
having the formula [A] previously mentioned as the antioxidant,
0.2 wt. % of 1-3,2*4-di(paramethylbenzylidene)sorbitol ("Gel All MD", New
Japan Chemical) as the organic nucleating agent,
0.1 wt. % of glycerine monostearate ester as the dripproofing agent,
0.1 wt. % of calcium stearyl lactate and 0.05 wt. % of erucic acid amide as
the lubricant,
0.3 wt. % of magnesium stearate, and 0.2 wt. % of A-type zeolite.
Using the above homopolyethylene resin composition, the container body for
a photographic film shown in FIG. 10 was formed by using a toggle type
injection molding machine ("NESTAL", Sumitomo Heavy Industries) with a hot
runner type mold having a number of cavities of 24 at a mold clamping
pressure of 150 t at a resin temperature of 200.degree. C.
The inner surface was roughened by forming longitudinal ribs 0.25 .mu.m in
height, and the outer surface was roughened by forming lattice ribs 0.15
.mu.m in height.
The haze of the container body was excellent of 31%, and the design, print
and the like of the cartridge for a photographic film in the container
body could be seen clearly. The photographic properties of photographic
photosensitive materials were excellent, and the occurrence of fogging and
sensitivity deviation was rare. Thermal degradation of resin and additives
was small, and coloring troubles and lump generation were rare. Fatal
molding troubles did not occur, and continuous unmanned injection molding
was possible for a long period. Appearance was also excellent. Because of
using a resin having a high crystallinity of 97%, rigidity was great, and
wear resistance was excellent. The cooling time after molding could be
sharply shortened, and 6 second molding became possible. By adding the
effects of roughening the inner peripheral surface of the container body
by forming longitudinal ribs 0.25 .mu.m in height, buckling and bottom
sink mark did not occur at all, and the pop sould did not generate at the
time of extracting the mold core from the container body. Dropping
strength under low temperature conditions was improved, and cracking did
not occur (0%) by dropping the container body containing a ISO
photographic speed 400 photographic speed negative film of 36 exposures
sealed by attaching a cap from 5 m height to concrete floor at 0.degree.
C.
Moreover, when a photographic film cartridge was taken out from the
container after storing in a cold storage room for 1 year, foreign odor
was decreased to the degree of not finding, and water drops on the
peripheral wall of the container body were not observed. Degradation of
photographic performance was within 5% which does not affect photographing
at all.
Example 9
A container body corresponding to FIG. 10 was molded.
The molding resin composition was a homopolyethylene resin composition
consisting of;
98.3 wt. % of high density homopolyethylene resin having a MFR (ASTM
D-1238) of 18 g/10 minutes, a density (ASTM D-1505) of 0.963 g/cm.sup.3, a
crystallinity (X-ray diffraction method) of 92%, a haze (ASTM D-1003) of
65%, a bending elastic modulus (ASTM D-790) of 12,800 kg/cm.sup.2, a Shore
hardness (ASTM D-2240) of 70D, a notched Izod impact strength (ASTM D-256)
at 23.degree. C. of 4.7 kg.cm/cm, a Vicat softening point (ASTM D-1525) of
133.degree. C., a melting point (ASTM D-2117) of 140.degree. C. and an
elongation at rupture (ASTM D-638) of more than 500%.
0.3 wt. % of A-type zeolite as an inorganic substance having ion-exchange
ability,
0.1 wt. % of a hindered phenolic antioxidant of pentaerythrityl-tetrakis
[3-(3.5-di-t-butyl-4-hydroxyphenyl) propionate]methane, and 0.05 wt. % of
a phosphorus-containing antioxidant of tris(2,4-di-t-butylphenyl)
phosphite as the antioxidant,
0.2 wt. % of 1.3,2.4-di(paramethylbenzylidene)sorbitol ("Gel All MD", New
Japan Chemical) as the organic nucleating agent,
0.1 wt. % of glycerine monostearate ester as the dripproofing agent,
0.1 wt. % of calcium stearyl lactate and 0.05 wt. % of erucic acid amide as
the lubricant, and
0.8 wt. % of oil furnace carbon black which is an oil absorption material
having a mean particle size of 21 .mu.m, a pH of 8.0, an oil absorption
value of 87 ml/100 g, a sulfur content of 0.3 wt. % and a volatile
component content of 0.3 wt. % of which the surface had been coated with
0.2 wt. % of zinc stearate.
Using the above homopolyethylene resin composition, the container body for
a photographic film shown in FIG. 10 was formed by using a toggle type
injection molding machine ("NESTAL", Sumitomo Heavy Industries) with a hot
runner type mold having a number of cavities of 24 at a mold clamping
pressure of 150 t at a resin temperature of 200.degree. C.
The inner surface was roughened by forming longitudinal ribs 0.25 .mu.m in
height, and the outer surface was roughened by forming lattice ribs 0.15
.mu.m in height.
In the container body uniform dispersibility of carbon black was improved,
and the photographic properties of photographic photosensitive materials
were excellent, and the occurrence of fogging and sensitivity deviation
was rare. Since a high density homopolyethylene resin having a high haze
was used, light-shielding ability was excellent. Coloring troubles did not
occur at all, and lump generation were rare. Fatal molding troubles did
not occur, and continuous unmanned injection molding was possible for a
long period. Appearance was also excellent. Because of using a resin
having a high crystallinity of 92%, rigidity was great, and wear
resistance was excellent. The cooling time after molding could be
shortened, and 7 second molding became possible. By adding the effects of
roughening the inner peripheral surface of the container body by forming
longitudinal ribs 0.25 .mu.m in height, buckling and bottom sink mark did
not occur at all, and the pop sould did not generate at the time of
extracting the mold core from the container body.
Example 10
A spool for a photographic film corresponding to FIG. 13 was molded.
The molding resin composition consisted of;
100 parts by weight of propylene-ethylene random copolymer resin consisting
of 70 parts by weight of propylene-ethylene random copolymer resin
composed of 98 wt. % of propylene and 2 wt. % of ethylene having a MFR of
40 g/10 minutes, a density of 0.90 g/cm.sup.3, a crystallinity of 95%, a
bending elastic modulus (ASTM D-790) of 12,500 kg.multidot.cm/cm,
molecular weight distribution (weight average molecular weight/number
average molecular weight, MW/MN) of 4.5, 29.5 parts by weight of low
pressure vapor process ethylene-butene-1 copolymer resin composed of 96
wt. % of ethylene and 4 wt. % of butene-1 having a MFR of 25 g/10 minutes,
a density of 0.925 g/cm.sup.3, an Olsen rigidity of 2,800 kg/cm.sup.2
(ASTM D-747) and a molecular weight distribution (weight average molecular
weight/number average molecular weight) of 3.5, 0.10 part by weight of
lubricant of erucic acid amide, 0.2 part by weight of calcium
hydroxystrearate, and 0.2 part by weight of antistatic agent of
monoglyceride stearate having a monoglyceride content of 95%,
0.10 part by weight of vitamin E ((.alpha.-tocopherol) as the antioxidant,
0.05 part by weight of a hindered phenolic antioxidant of
2,6-di-tert-butyl-p-cresol (BHT), and
0.3 part by weight of calcium carbonate of which the surface had been
treated with 0.2 part by weight of dimethylpolysiloxane as the inorganic
nucleating agent.
Using the above resin composition, the spool for a photographic film shown
in FIG. 13 was formed by using an injection molding machine with a hot
runner type mold having a number of cavities of 24 at a mold clamping
pressure of 150 t at a resin temperature of 205.degree. C. at a molding
cycle of 8 seconds.
In the spool for a photographic film, fatal molding troubles, such as
coloring trouble, short shot and defective light-shielding occurred
rarely. Slipping character was very excellent, and taking out from the
mold was excellent. Deformation did not occur, and continuous unmanned
injection molding became possible for a long period. In the conventional
spool for a photographic film made of polystyrene resin, surfactant was
coated on the flange portion in order to decrease the extending torque of
photographic film. Compared with the conventional spool, the spool of this
example was excellent in shorter molding cycle, less occurrence of
abrasion, better slipping character resulting in the decrease of the
extension torque of photographic film. The above properties were
particularly effective for automatic winding photographic film camera
using an electrical cell, such as a sharp decrease of winding stop during
photographing and a sharp decrease of the consumption of electrical cell.
Moreover, chemical resistance and solvent resistance were remarkably
improved. Thus, the spool was preferable because of being used in
development processing stations wherein various agents are used and in the
world having a wide temperature variation.
Unexpectedly, fogging of photographic film was decreased by 0.03 in
density, and light-shielding ability was improved by 15%, i.e. the same
light-shielding ability can be ensured by decreasing light-shielding
material in an amount of 15%. Uniform dispersibility of light-shielding
material was improved, and sink at the thickened part, warpage of flange
and a great mold shrinkage, which occurred in the case of using a
conventional crystalline resin of propylene-ethylene random copolymer
resin, were improved to the degree of no problem.
As mentioned above, the spool was excellent, and various properties were
improved with rare occurrence of bleeding out of lubricant and antistatic
agent. The reason is considered that the generation of aldehydes generated
through the decomposition of resin by heat or oxygen adversely affecting
photographic film, is decreased by the synergistic effect of specific
furnace carbon black and vitamin E, that light-shielding ability is
improved by the coloring of vitamin E, and that the mold shrinkage is made
small by combining propylene-ethylene random copolymer resin and
ethylene-butene-1 copolymer resin, having a small molecular weight
distribution resulting in the decrease of sink and flange warpage.
Example 11
A cartridge for a photographic film made of resin corresponding to FIG. 14
was molded.
Using the resin composition of Example 10, the cartridge was molded by
injection molding.
The cartridge was excellent in various properties similar to Example 10. It
was particularly excellent in slipping character, wear resistance and
injection moldability, and both torques of extending and winding
photographic film were small. Stop of the extending and winding
photographic film did not occur during photographing at all.
Example 12
A coextruded double layer film corresponding to FIG. 3 consisting of a
light-shielding thermoplastic resin film layer 1a and a light-shielding
thermoplastic resin film layer 2a was molded.
The light-shielding thermoplastic resin film layer 1a consisted of a L-LDPE
resin composition consisting of 18 wt. % of homopolyethylene resin having
a molecular weight distribution (MW/MN) of 7.6, a MFR of 0.6 g/10 minutes,
a density of 0.925 g/cm.sup.3, a crystallinity of 71%, 76.7 wt. % of
ethylene-butene-1 random copolymer resin having a MFR of 5.0 g/10 minutes,
a density of 0.88 g/cm.sup.3, a molecular weight distribution (MW/MN) of
3.6, a crystallinity of 35%, an ethylene unit content of 80 mol. % and a
butene-1 unit content of 20 mol. %, 3 wt. % of furnace carbon black having
a pH of 7.0, a mean particle size of 25 .mu.m, a weight loss or drying
under bone-dry conditions of 0.08 wt. % of which the surface had been
coated with magnesium stearate 0.05 wt. % of erucic acid amide, 0.05 wt. %
of vitamin E and 0.05 wt. % of tetrakis
[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, and
had a thickness of 50 .mu.m with black appearance.
The light-shielding thermoplastic resin film layer 2a consisted of a L-LDPE
resin composition consisting of 20 wt. % of homopolyethylene resin having
a molecular weight distribution (MW/MN) of 7.6, a MFR of 1.0 g/10 minutes,
a density of 0.945 g/cm.sup.3 and a crystallinity of 78%, 73.5 wt. % of
ethylene-octent-1 copolymer resin having a MFR of 2.5 g/10 minutes, a
density of 0.92 g/cm.sup.3, a crystallinity of 53%, a molecular weight
distribution (MW/MN) of 3.3, an ethylene unit content of 95 mol. % and an
octene-1 unit content of 5 mol. %, 6 wt. % of titanium dioxide having a
weight loss on drying under bone-dry conditions of 0.15 wt. % of which the
surface had been coated with a divalent alcohol, 0.05 wt. % of silica, 0.2
wt. % of zinc stearate and 0.1 wt. % of vitamin E, and had a thickness of
50 .mu.m with white appearance.
The coextruded double layer film 100 .mu.m in total thickness was molded by
the inflation process at a blow-up ratio of 1.5.
The coextruded double layer inflation film was excellent in physical
strength, heat sealing properties, photographic properties,
light-shielding ability, flatness, moldability and appearance. The
discrimination of the obverse side and the reverse side and finding of a
sealing bag having a white appearance made by heat sealing where the black
layer was disposed on the inside were possible even under a safety light.
When the bag was left under the sunlight, temperature rise did not occur
on both of the inside and the outside, and quality of photographic
photosensitive materials contained therein was not degraded. Stacking of
the bag was possible. Since vitamin E was combined with light-shielding
material, light-shielding ability was improved by 15% or more. Physical
strength and heat seal strength were great. Adverse affects on
photographic properties, such as sensitivity deviation and fogging, of
photographic photosensitive materials could be decrease by the prevention
of resin decomposition.
Example 13
A container body corresponding to FIG. 10 was molded.
The molding resin composition was a polypropylene-ethylene random copolymer
resin composition consisting of 8.66 wt. % of a masterbatch containing 35%
of titanium dioxide prepared by dispersing 3 wt. % of titanium dioxide
having a weight loss on drying under bone-dry conditions of 0.2 wt. %,
0.15 wt. % of di-(p-methylbenzylidene)sorbitol and 0.01 wt. % of
o-methylbenzylidene-p-methylbenzylidene-sorbitol, of which the surfaces
were coated with 0.5 wt. % of calcium stearate, into 5 wt. % of a resin
mixture of low density homopolyetyylene resin and polyethylene wax, 90.54
wt. % of propylene-ethylene random copolymer resin having a MFR of 40 g/10
minutes, a density of 0.90 g/cm.sup.3, a bending elastic modulus (ASTM
D-790) of 10,700 kg/cm.sup.2, a Rockwell hardness (ASTM D-785) of 88R, a
molecular weight distribution (MW/MN) of 3.7, a propylene unit content of
96.7 wt. % and an ethylene unit content of 3.5 wt. %, 0.05 wt. % of oleic
acid amide, 0.10 wt. % of a hindered phenolic antioxidant of tetrakis
[methylene-3-(3.5-di-tert-butyl-4-hydroxyphenyl)propionate] methane, 0.05
wt. % of a phosphorus-containing antioxidant of trinonylphenylphosphite,
0.1 wt. % of an ultraviolet absorber of 2-hydroxy-4-octoxybenzophenone and
0.5 wt. % of diglycerine monostearate as the dripproofing agent.
Using the above polypropylene-ethyene random copolymer resin composition,
the container body for a photographic film cartridge was formed by
injection molding using an injection molding machine using a mold having a
number of cavities of 24 at a mold clamping pressure of 150 t at a resin
temperature of 220.degree. C., a cooling water temperature of 20.degree.
C. and a molding cycle of 7 seconds.
The peripheral wall thickness of the container body was thinned to 0.7 mm
from 1 mm.
Even though the temperature of the molded container body was 45.degree. C.
at the time of taking out, deformation, such as buckling and bottom sink
mark, and abrasion did not occur, and continuous unmanned molding was
possible for a long period. White appearance was excellent.
In the container body for a photographic film cartridge having white
appearance, molding cycle was very rapid 7 seconds in spite of multi
cavity molding capable of molding 24 pieces per once, and productivity was
excellent. Since deformation did not occur even at a high taking out
temperature of around 45.degree. C., Rockwell hardness was improved to 98R
by raising crystallinity. As a result, abrasion and abrasion dust were not
generated by conveying the container body pneumatically at a high speed or
putting a photographic film cartridge therein and sealing by fitting a
cap.
Moreover, after storing in a cold storage room at 18.degree. C. for 1 year,
bleeding out was rarely observed, and adhesion of water drops was also not
observed. Even though the container body was left in a automobile car
under the sunlight, thermal deformation of the container body and the
spool on which a photographic film was wound placed in the container did
not occur. Printability was excellent. Even though the container body was
displayed in a store as it is, discoloration and thermal deformation did
not occur, and adhesion of dust was small. Photographic properties were
excellent, and fogging was sharply decreased from 0.07 to 0.02 compared
with the container body blended with the light-shielding material of which
the surface-coating was not done.
Since the peripheral wall was thinned to 0.7 mm the leading end of
photographic film could be easily placed therein, and insertion ability in
an automatic apparatus was excellent. The resin gate portion was thickened
by 30% than the mean thickness of the bottom portion. As a result, even
though the gate portion was scraped at the time of extracting from a mold,
the gate portion was kept almost the same thickness as the other bottom
portion resulting in ensuring moistureproofness and light-shielding.
Furthermore, Rockwell hardness was sharply improved, and as a result, not
only abrasion was decreased but also cooling time after molding could be
shorted by taking out at a high temperature around 40.degree. C. resulting
in sharp shortening of molding cycle. Molding troubles, such as
deformation and resin remaining at gate, were rare, and unmanned molding
was possible.
Example 14
A container body corresponding to FIG. 11 was molded. The thickness of the
peripheral wall portion was thinned to 0.7 mm from 1 mm. The inside
diameter near the bottom was adjusted to about the outer diameter of the
cartridge at the exit port portion of photographic film, and the
peripheral wall was tapered so as to have an inside diameter at the
opening greater than the bottom by 1.5 mm. The container body was
stackable.
The molding resin consisted of 77.5 wt. % of propylene-ethylene random
copolymer resin having a MFR of 30 g/10 minutes, a density of 0.900
g/cm.sup.3 and a crystallinity of 87%, 2.0 wt. % of aluminum powder of
which the surface had been coated with 0.05 wt. % of oleic acid amide and
0.2 wt. % of magnesium stearate, 0.05 wt. % of a hindered phenolic
antioxidant of tetrakis
[methylene-3(3.5-di-tert-butyl-4-hydroxyphenyl)propionate] methane and
0.05 wt. % of n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)
propionate as the antioxidant, 20 wt. % of ethylene-butene-1 copolymer
resin having a MFR of 23 g/10 minutes, a density of 0.905 g/cm.sup.3 and a
crystallinity of 23% as the low crystallinity resin, and 0.15 wt. % of 1
3,2 4-di-(methylbenzylidene)sorbitol of which the surface had been coated
with magnesium stearate as the organic nucleating agent.
Using the above polypropylene resin composition, the container body for a
photographic film cartridge was formed by injection molding using an
injection molding machine using a mold having a number of cavities of 24
at a mold clamping pressure of 150 t at a resin temperature of 210.degree.
C. at a molding cycle of 8 seconds.
In the molded container bodies, fatal molding troubles, such as coloring
and short shot, was rare. Moreover, deformation also did not occur, and
continuous unmanned injection molding became possible for a long period.
The molded product of the container body for a photographic film cartridge
was excellent in shortening of molding cycle, in high speed pneumatic
conveying due to good slipping between the container bodies, resistance to
abrasion, antistatic properties, little adhesion of dust, and insertion of
a photographic film cartridge into the container body. Moreover,
appearance was silver and very excellent, and dropping strength from 5 m
height to concrete floor was very great, and particularly, dropping impact
strength at a low temperature condition of not more than 0.degree. C. was
very excellent by the synergistic effect of the combination of aluminum
powder and ethylene-butene-1 copolymer resin, and the occurrence of cracks
was 0% compared with 6% of the container body for a photographic film
cartridge of Comparative Example 4 not containing aluminum powder and
ethyene-butene-1 copolymer resin. After storing at 18.degree. C. for 1
year, bleeding out of the lubricant of oleic acid amide and magnesium
stearate onto the surface of the container body was small, and greasiness,
dust adhesion and white powder generation were rare. Appearance was
excellent, and impact strength, slipping character and antistatic
properties were also excellent. Unexpectedly, it was found that mold
shrinkage caused by the gradual proceeding of crystallization of
polypropylene resin is decreased by blending the surface-coated aluminum
powder and ethylene-butene-1 copolymer resin. Moreover, even when the
container body was left under the sunlight for 5 hours in a form of sealed
container, heat absorption was small, and deformation did not occur.
Temperature rise on the inside of the container was small, and degradation
of the quality of photographic film did not occur.
Example 15
A container body corresponding to FIG. 10 was molded.
Using a light-shielding propylene-ethylene random copolymer resin
composition composed of the polypropylene resin composition of Example 14
wherein the content of ethylene-butene-1 copolymer resin was decreased
from 20 wt. % to 19 wt. %, and 3 wt. % of furnace carbon black having a
mean particle size of 20 .mu.m and a pH of 7.0 of which the surface was
coated with oleic acid amide and zinc stearate as the light-shielding
material, the container body was molded using the same injection molding
machine and the same mold as Example 13 at a resin temperature of
210.degree. C. at a molding cycle of 6 seconds.
In molding the container body for a photographic film cartridge, fatal
molding troubles did not occur, and continuous unmanned injection molding
was possible for a long period. Appearance was also excellent. In the
molded product of the container body for a photographic film cartridge,
deformation, such as buckling or bottom sink mark did not occur, even
though the molding cycle was shortened by 9 second form Comparative
Example 4. The occurrence of coloring trouble was rare. Dropping strength
was very greater than Comparative Example 4, and the generation of
cracking was 0% at ordinary temperature (20.degree. C.). Dropping strength
under low temperature conditions at not more than 0.degree. C. was greater
than Comparative Example 4, and the generation of cracking was decreased
from 6% to 0%. Nevertheless the container body was black opaque, even
though the container body was left under the sunlight for 3 hours, thermal
deformation did not occur. The container body was excellent in
heat-shielding, and temperature rise of the inside of container was not
great compared with Comparative Example 4. As a result, thermal
deformation of the spool contained in the cartridge did not occur, and
degradation of photographic properties of the photographic film scarcely
occurred. Since the color was black, light-shielding ability was
excellent, leak of light from the exit port of photographic film cartridge
was none. After storing at 18.degree. C. for 1 year, substances adversely
affecting photographic film did not generate, and fogging and sensitivity
deviation did not occur. Moreover, bleeding out of lubricant, antioxidant,
nucleating agent and the like was small by the adsorption on carbon black,
and greasiness, dust adhesion and white powder generation were less than
Example 13. Moreover, they could not be seen by the synergistic effect of
black appearance.
Example 16
A container corresponding to FIG. 12 was molded which was a cap-body
integrated type square container for a photographic film cartridge wherein
the cap was integrated to the container body through a hinge.
Using the same propylene-ethyene random copolymer resin composition as
Example 14, the container was molded by injection molding using an
experimental mold having one cavity.
The properties of the molded container were excellent similar to Example
14. Moreover, since the form was square, the container had stacking
ability and atore displaying ability. Moreover, decorated paper casket
could be omitted, and corporation identity (CI) mark and various prints
were clear because of a white opaque container. As described in Example 6
and Example 14, even though the container was displayed at a store, the
white opaque body reflected the sunlight, and deformation of the container
did not occur. Temperature rise of the inside of the container was small.
As a result, thermal deformation of the spool contained in the cartridge
was rare, and degradation of photographic properties of the photographic
film scarcely occurred. Antistatic ability was excellent, and bleeding out
of the lubricant, the antioxidant and the nucleating agent onto the
surface of the container was small because of containing an oil absorption
material of titanium dioxide. Adhesion of dust was small. Industrial waste
could be decreased, and recycling use was many. Moreover, by blending a
suitable amount of antioxidant, thermal degradation of resin and additives
can be prevented, and the generation of substances adversely affecting
photographic film can be decreased.
Comparative Example 4
A container body corresponding to FIG. 10 was molded.
Using the same propylene-ethylene random copolymer resin composition as
Example 14, except that 0.1 wt. % of two kinds of the hindered phenolic
antioxidant, 2.0 wt. % of aluminum powder, 0.05 wt. % of oleic acid amide
and 0.2 wt. % of magnesium stearate for the surface coating of the
nucleating agent and 30 wt. % of the ethylene-butene-1 copolymer resin
were omitted, and the content of the propylene-ethylene random copolymer
resin was increased from 77.5 to 97.85 wt. %, the container body was
molded using the same molding machine and the same mold as Example 14 at a
molding cycle of 8 seconds.
The container body had excellent properties, and dimensional accuracy
almost similar to Example 13, except that dropping strength under low
temperature conditions at not more than 0.degree. C. and appearance were
inferior, immediately after molding. However, after storing in a cold
storage room at 18.degree. C. for 1 year, crystallization proceeded, and
dropping strength at ordinary temperature was inferior to Example 13. When
dropped from 5 m height to concrete floor at 0.degree. C., cracking
occurred at a rate of 6%. The most important problem was inferior
dispersibility of aluminum powder resulting in the degradation of
appearance. Molding cycle was not less than twice Example 13 of 15 seconds
or more, and buckling, short shot and bottom sink mark occasionally
occurred. Slipping character was inferior and pop sound generated at the
time of extracting the mold core from the container body. Since hindered
phenolic antioxidant was not added, the resin was decomposed to produce
aldehydes and the like at retanded portions during continuous molding for
a long period, and they adversely affected photographic photosensitive
materials, such as fogging or sensitivity deviation. Resin yellowing
occurred resulting in the occurrence of coloring troubles, and lumps were
generated to induce gate clogging and short shot problem. Thus, unmanned
continuous molding was difficult.
Example 17
A spool for a photographic film corresponding to FIG. 13 was molded.
The molding resin composition consisted of 70 wt. % of propylene-ethylene
random copolymer resin composed of 98 wt. % of propylene and 2 wt. % of
ethylene having a MFR of 40 g/10 minutes, a density of 0.90 g/cm.sup.3, a
crystallinity of 95%, a bending elastic modulus (ASTM D-790) of 12,500
kg/cm.sup.2, a molecular weight distribution (weight average molecular
weight/number average molecular weight, MW/MN) of 4.5, 26.85 wt. % of low
pressure vapor process ethylene-butene-1 copolymer resin composed of 96
wt. N of ethylene and 4 wt. % of butene-1 having a MFR of 25 g/10 minutes,
a density of 0.925 g/cm.sup.3, an Olsen rigidity (ASTM D-747) of 2,800
kg/cm.sup.2 and a molecular weight distribution (weight average molecular
weight/number average molecular weight) of 3.5,2 wt. % of furnace carbon
black having a mean particle size of 20 m.mu. and a pH of 7.0 of which the
surface had been coated with 0.10 wt. % of a lubricant of erucic acid
amide, 0.2 wt. %. of calcium hydroxystrearate, and 0.2 wt. % of antistatic
agent of monoglyceride stearate having a monoglyceride content of 95%,
0.10 wt. % of vitamin E (.alpha.-tocopherol) as the antioxidant, 0.05 wt.
% of a hindered phenolic antioxidant of 2,6-di-tert-butyl-p-cresol (BHT),
and 0.3 wt. % of calcium carbonate of which the surface had been treated
with 0.2 wt. % of dimethylpolysiloxane as the inorganic nucleating agent.
Using the above resin composition, the spool for a photographic film shown
in FIG. 13 was formed by using an injection molding machine with a hot
runner type mold having a number of cavities of 24 at a mold clamping
pressure of 150 t at a resin temperature of 205.degree. C. at a molding
cycle of 8 seconds.
In the spool for a photographic film, fatal molding troubles, such as
coloring trouble, short shot and defective light-shielding occurred
rarely. Slipping character was very excellent, and taking out from the
mold was excellent. Deformation did not occur, and continuous unmanned
injection molding became possible for a long period. In the conventional
spool for a photographic film made of polystyrene resin, surfactant was
coated on the flange portion in order to decrease the extending torque of
photographic film. Compared with the conventional spool, the spool of this
example was excellent in shorter molding cycle, less occurrence of
abrasion, better slipping character resulting in the decrease of the
extension torque of photographic film. The above properties were
particularly effective for automatic winding photographic film camera
using an electrical cell, such as a sharp decrease of winding stop during
photographing and a sharp decrease of the consumption of electrical cell.
Moreover, chemical resistance and solvent resistance were remarkably
improved. Thus, the spool was preferable because of being used in
development processing stations wherein various agents are used and in the
world having a wide temperature variation.
Unexpectedly, fogging of photographic film was decreased by 0.03 in
density, and light-shielding ability was improved by 15%, i.e. the same
light-shielding ability can be ensured by decreasing light-shielding
material in an amount of 15%. Uniform dispersibility of light-shielding
material was improved, and sink at the thickened part, warpage of flange
and a great mold shrinkage, which occurred in the case of using a
conventional crystalline resin of propylene-ethylene random copolymer
resin, were improved to the degree of no problem.
As mentioned above, the spool was excellent, and various properties were
improved with rare occurrence of bleeding out of lubricant and antistatic
agent. The reason is considered that the generation of aldehydes generated
through the decomposition of resin by heat or oxygen adversely affecting
photographic film, is decreased by the synergistic effect of specific
furnace carbon black and vitamin E, that light-shielding ability is
improved by the coloring of vitamin E, and that the mold shrinkage is made
small by combining propylene-ethylene random copolymer resin and
ethylene-butene-1 copolymer resin, having a small molecular weight
distribution resulting in the decrease of sink and flange warpage.
Example 18
A cartridge for a photographic film corresponding to FIG. 14 was molded.
Using the resin composition of Example 17, the cartridge was molded by
injection molding.
The cartridge was excellent in various properties similar to Example 17. It
was particularly excellent in slipping character, wear resistance and
injection moldability, and both torques of extending and winding
photographic film were small. Stop of the extending and winding
photographic film did not occur during photographing at all.
Example 19
81.62 wt. % of high density homopolyethylene resin having a MFR of 0.3 g/10
minutes, a density of 0.95 g/cm.sup.3 and a Vicat softening point of
128.degree. C., 0.05 wt. % of melissyl cerotate ester, 0.3 wt. % of
magnesium stearate, 3 wt. % of furnace carbon black having a pH of 7.0, a
mean particle size (microscopy) of 20 m.mu., an oil absorption value of 80
ml/100 g, a volatile component content of 0.7%, a sulfur component content
of 0.61% (containing 0.02% of free sulfur components), 0.03 wt. % of a
hindered phenolic antioxidant of tetrakis
[methylene-3-(3.5-di-tert-butyl-4-hydroxyphenyl)propionate]methane and 15
wt. % of powder of ethylene-butene-1 random copolymer resin having a MFR
of 0.7 g/10 minutes, a density of 0.92 g/cm.sup.3 and a softening point of
100.degree. C. were sufficiently blended by a Henschel mixer, and extruded
in strand by a double shaft kneader (Ikegai Corp.) at a resin temperature
of 210.degree. C., and pelletized into cylindrical pellet 3 mm in diameter
6 mm in length by a pelletizer.
Using the pellets, a light-shielding inflation film 100 .mu.m in thickness
was molded by an inflation film molding machine (Placo Co.) having a ring
die 200 mm.phi. with a lip clearance of 1.1 mm at a blow-up ratio of 1.2
as the guide member of FIG. 18, and a light-shielding inflation film 70
.mu.m in thickness was molded as the film cover member. As the roll
photographic photosensitive material, color printing paper was used. The
light-shielding inflation film 70 .mu.m in thickness of the cover member
had a molecular orientation in the longitudinal direction having a tear
strength in the lateral direction of 967 g/a tear strength in the
longitudinal direction of 136 g=7.1. As a result, by arranging the
longitudinal direction in the arrow direction in FIG. 18, the cover member
can be torn at the joined portion by pulling the guide member from the
automatic developing apparatus after loading the sealed package for light
room loading.
Since both of the cover member and the guide member were made of the same
resin composition, the joining therebetween can be conducted by melt
fusion. It is also possible to join the guide member to the roll
photosensitive material by melt fusion, and the sealed light-shielding
package can be formed simply. As a result of using melissyl cerotate
ester, motor load was decreased by 20%, and film moldability was
excellent. The thickness difference of inflation film was 6 .mu.m less
than one third of the inflation film of not blending of 22 .mu.m.
Wrinkling did not occur at all, and light-shielding, physical strength and
appearance were excellent.
Example 20
Using a white ethylene-butene-1 random copolymer resin composition
consisting of 94.55 wt. % of ethylene-butene-1 random copolymer resin
having a MFR of 20 g/10 minutes, a density of 0.950 g/cm.sup.3, an Izod
impact strength of 9 kg.multidot.cm/cm, an Olsen rigidity of 7,500
kg/cm.sup.2 and a Vicat softening point of 115.degree. C., 0.05 wt. % of
melissyl montanate ester, 0.2 wt. % of zinc stearate, 5 wt. % of titanium
dioxide of which the surface had been coated with hydrous aluminum oxide
and 0.2 wt. % of 1.3,2.4-diheptanylidenesorbitol, a cap-body integrated
type case for a photographic film corresponding to FIG. 16 was formed by
injection molding.
The contain did not adversely affect photographic photosensitive materials,
and dropping strength was very excellent. Since the appearance was white,
it could be found under a safety light. Even when it was left under the
sunlight for two hours, temperature rise on the inside of the container
was small, and degradation of the quality of photographic photosensitive
materials did not occur. Water drops in the container were rarely
observed. The motor load of screw was decreased by more than 20%, and the
dispersion of thickness was small. Sealability and fitting ability were
excellent, and printability was also excellent. It was possible to omitt
the decorated casket by applying various sealing means for proving the
virginity. After use, it could be use as a container for various small
articles. Resin recycling was also possible. Since the body and the were
made of the same resin composition, their separation was not necessary,
and they could be pelletized as it is. Moreover, the decrease of physical
strength by the pelletization was small.
Example 21
A container body corresponding to FIG. 10 was molded.
The molding resin composition was a homopolyethylene resin composition
consisting of;
98.65 wt. % of high density homopolyethylene resin having a MFR (ASTM
D-1238) of 20 g/10 minutes, a density (ASTM D-1505) of 0.963 g/cm.sup.3, a
bending elastic modulus (ASTM D-790) of 15,400 kg/cm.sup.2, a Shore
hardness (ASTM D-2240) of 71D, a notched Izod impact strength (ASTM D-256)
at 23.degree. C. of 3.5 kg.multidot.cm/cm, a Vicat softening point (ASTM
D-1525) of 124.degree. C., a melting point (ASTM D-2117) of 134.degree. C.
and an elongation at rupture (ASTM D-638) of 387%, 0.1 wt. % of a hindered
phenolic antioxidant of pentaerythrityl-tetrakis
[3-(3.5-di-t-butyl-4-hydroxyphenyl) propionate] methane, and 0.05 wt. % of
a phosphorus-containing antioxidant of tris(2,4-di-t-butylphenyl)
phosphite as the antioxidant,
0.2 wt. % of 1.3,2.4-di(paramethylbenzylidene)sorbitol ("Gel All MD", New
Japan Chemical) as the organic nucleating agent,
1 wt. % of oil furnace carbon black having a mean particle size of 21
m.mu., a pH of 8.0, an oil absorption value of 87 ml/100 g, a sulfur
content of 0.3 wt. % and a volatile component content of 0.3 wt. % of
which the surface had been coated with 0.2 wt. % of zinc stearate, and 0.2
wt. % of A-type zeolite.
Using the above homopolyethylene resin composition, the container body for
a photographic film shown in FIG. 10 was formed by using a toggle type
injection molding machine ("NESTAL", Sumitomo Heavy Industries) with a hot
runner type mold having a number of cavities of 24 at a mold clamping
pressure of 150 t at a resin temperature of 200.degree. C.
The inner surface was roughened by forming longitudinal ribs 0.25 .mu.m in
height, and the outer surface was roughened by forming lattice ribs 0.15
.mu.m in height.
In the container body, uniform dispersibility of carbon black was improved,
and the photographic properties of photographic photosensitive materials
were excellent, and the occurrence of fogging and sensitivity deviation
was rare. Light-shielding ability was excellent. Coloring troubles did not
occur at all, and lump generation were rare. Fatal molding troubles did
not occur, and continuous unmanned injection molding was possible for a
long period. Appearance was also excellent. By adding the effects of
roughening the inner peripheral surface of the container body by forming
longitudinal ribs 0.25 .mu.m in height, buckling and bottom sink mark did
not occur at all, and the pop sound did not generate at the time of
extracting the mold core from the container body.
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